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Blackmond, Donna
Faculty Member
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Positions
- 2018 - co-Chair, Chemistry , Scripps Research
- 2009 - Professor, Chemistry , Scripps Research
- 2009 - Faculty Member, Skaggs Graduate School of Chemical and Biological Sciences , Scripps Research
- 2004 - 2010 Chair in Catalysis, Imperial College London
- 2004 - 2010 Professor of Chemistry, Imperial College London
- 2004 - 2010 Professor of Chemical Engineering, Imperial College London
- 1999 - 2003 Professor and Chair in Physical Chemistry, University of Hull
- 1996 - 1999 Group Leader, Max Planck Institute for Coal Research
- 1992 - 1999 Adjunct Professor of Chemical Engineering, University of Pittsburgh
- 1995 - 1996 Professor of Technical Chemistry, University of Essen
- 1992 - 1995 Associate Director, Technical Operations, Merck & Co., Inc.
- 1989 - 1992 Associate Professor of Chemical Engineering and BP America Faculty Fellow, University of Pittsburgh
- 1984 - 1989 Assistant Professor of Chemical Engineering, University of Pittsburgh
Dr. Donna Blackmond focuses on mechanistic aspects of the synthesis of complex organic molecules by catalytic routes, particularly asymmetric catalysis with application in pharmaceutical processes. Her group also investigates nonlinear effects of catalyst enantiopurity in stoichiometric, catalytic and autocatalytic reactions. Another area of fundamental interest is in probing the origin of biological homochirality.
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Publications
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academic article
- Dechert-Schmitt, A. M., Garnsey, M. R., Wisniewska, H. M., Murray, J. I., Lee, T., Kung, D. W., Sach, N., Blackmond, D. G. Highly modular synthesis of 1,2-diketones via multicomponent coupling reactions of isocyanides as CO equivalents ACS Catalysis 2019 9:4508-4515 DOI:10.1021/acscatal.9b00581
- Blackmond, D. G. The origin of biological homochirality Cold Spring Harbor Perspectives in Biology 2019 11 DOI:10.1101/cshperspect.a032540 PMID:30824575
- Hill, D. E., Pei, Q. L., Zhang, E. X., Gage, J. R., Yu, J. Q., Blackmond, D. G. A general protocol for addressing speciation of the active catalyst applied to ligand-accelerated enantioselective C(sp(3))-H bond arylation ACS Catalysis 2018 8:1528-1531 DOI:10.1021/acscatal.8b00103
- Wang, J., Shang, M., Lundberg, H., Feu, K. S., Hecker, S. J., Qin, T., Blackmond, D. G., Baran, P. S. Cu-catalyzed decarboxylative borylation ACS Catalysis 2018 8:9537-9542 DOI:10.1021/acscatal.8b02928
- Mower, M. P., Blackmond, D. G. In-situ monitoring of enantiomeric excess during a catalytic kinetic resolution ACS Catalysis 2018 8:5977-5982 DOI:10.1021/acscatal.8b01411
- Wang, J., Lundberg, H., Asai, S., Martin-Acosta, P., Chen, J. S., Brown, S., Farrell, W., Dushin, R. G., O'Donnell, C. J., Ratnayake, A. S., Richardson, P., Liu, Z., et al. Kinetically guided radical-based synthesis of C(sp(3))-C(sp(3)) linkages on DNA Proceedings of the National Academy of Sciences of the United States of America 2018 115:E6404-E6410 DOI:10.1073/pnas.1806900115 PMID:29946037 PMCID:PMC6048552
- Hawbaker, N. A., Blackmond, D. G. Rationalization of asymmetric amplification via autocatalysis triggered by isotopically chiral molecules ACS Central Science 2018 4:776-780 DOI:10.1021/acscentsci.8b00297 PMID:29974074 PMCID:PMC6026777
- Plata, R. E., Hill, D. E., Haines, B. E., Musaev, D. G., Chu, L., Hickey, D. P., Sigman, M. S., Yu, J. Q., Blackmond, D. G. A role for Pd(IV) in catalytic enantioselective C-H functionalization with monoprotected amino acid ligands under mild conditions Journal of the American Chemical Society 2017 139:9238-9245 DOI:10.1021/jacs.7b03716 PMID:28605190
- Wagner, A. J., Zubarev, D. Y., Aspuru-Guzik, A., Blackmond, D. G. Chiral sugars drive enantioenrichment in prebiotic amino acid synthesis ACS Central Science 2017 3:322-328 DOI:10.1021/acscentsci.7b00085 PMID:28470050 PMCID:PMC5408343
- Hill, D. E., Bay, K. L., Yang, Y. F., Plata, R. E., Takise, R., Houk, K. N., Yu, J. Q., Blackmond, D. G. Dynamic ligand exchange as a mechanistic probe in Pd-catalyzed enantioselective C-H functionalization reactions using monoprotected amino acid ligands Journal of the American Chemical Society 2017 139:18500-18503 DOI:10.1021/jacs.7b11962 PMID:29215885
- Gherase, D., Hazen, R. M., Krishnamurthy, R., Blackmond, D. G. Mineral-induced enantioenrichment of tartaric acid Synlett 2017 28:89-92 DOI:10.1055/s-0036-1588912
- Liu, W. B., Schuman, D. P., Yang, Y. F., Toutov, A. A., Liang, Y., Klare, H. F. T., Nesnas, N., Oestreich, M., Blackmond, D. G., Virgil, S. C., Banerjee, S., Zare, R. N., et al. Potassium tert-butoxide-catalyzed dehydrogenative C-H silylation of heteroaromatics: A combined experimental and computational mechanistic study Journal of the American Chemical Society 2017 139:6867-6879 DOI:10.1021/jacs.6b13031 PMID:28403611
- Gallagher, W. P., Soumeillant, M., Chen, K., Fox, R. J., Hsiao, Y., Mack, B., Iyer, V., Fan, J., Zhu, J., Beutner, G., Silverman, S. M., Fanfair, D. D., et al. Preparation of the HIV attachment inhibitor BMS-663068. Part 7. Development of a regioselective ullmann-Goldberg-Buchwald reaction Organic Process Research & Development 2017 21:1156-1165 DOI:10.1021/acs.oprd.7b00191
- Masseroni, D., Mosca, S., Mower, M. P., Blackmond, D. G., Rebek Jr., J. Cavitands as reaction vessels and blocking groups for selective reactions in water Angewandte Chemie-International Edition 2016 55:8290-8293 DOI:10.1002/anie.201602355 PMID:27254667
- Hawbaker, N., Wittgrove, E., Christensen, B., Sach, N., Blackmond, D. G. Dispersion in compartmentalized flow systems: influence of flow patterns on reactivity Organic Process Research & Development 2016 20:465-473 DOI:10.1021/op500360w
- Bures, J., Armstrong, A., Blackmond, D. G. Explaining anomalies in enamine catalysis: "downstream species" as a new paradigm for stereocontrol Accounts of Chemical Research 2016 49:214-222 DOI:10.1021/acs.accounts.5b00394 PMID:26830669
- Stich, M., Ribo, J. M., Blackmond, D. G., Hochberg, D. Necessary conditions for the emergence of homochirality via autocatalytic self-replication Journal of Chemical Physics 2016 145 DOI:10.1063/1.4961021 PMID:27544091
- Wagner, A. J., Blackmond, D. G. The future of prebiotic chemistry ACS Central Science 2016 2:775-777 DOI:10.1021/acscentsci.6b00336 PMID:27924306 PMCID:PMC5126717
- Shi, Q., Mower, M. P., Blackmond, D. G., Rebek Jr., J. Water-soluble cavitands promote hydrolyses of long-chain diesters Proceedings of the National Academy of Sciences of the United States of America 2016 113:9199-9203 DOI:10.1073/pnas.1610006113 PMID:27482089 PMCID:PMC4995975
- Blackmond, D. G. Kinetic profiling of catalytic organic reactions as a mechanistic tool Journal of the American Chemical Society 2015 137:10852-10866 DOI:10.1021/jacs.5b05841 PMID:26285166
- Ji, Y., Benkovics, T., Beutner, G. L., Sfouggatakis, C., Eastgate, M. D., Blackmond, D. G. Mechanistic insights into the vanadium-catalyzed Achmatowicz rearrangement of furfurol Journal of Organic Chemistry 2015 80:1696-1702 DOI:10.1021/jo502641d PMID:25562708
- Mower, M. P., Blackmond, D. G. Mechanistic rationalization of unusual sigmoidal kinetic profiles in the Machetti-De Sarlo cycloaddition reaction Journal of the American Chemical Society 2015 137:2386-2391 DOI:10.1021/ja512753v PMID:25611219
- Ji, Y., Plata, R. E., Regens, C. S., Hay, M., Schmidt, M., Razler, T., Qiu, Y., Geng, P., Hsiao, Y., Rosner, T., Eastgate, M. D., Blackmond, D. G. Mono-oxidation of bidentate bis-phosphines in catalyst activation: kinetic and mechanistic studies of a Pd/xantphos-catalyzed C-H functionalization Journal of the American Chemical Society 2015 137:13272-13281 DOI:10.1021/jacs.5b01913 PMID:26461028
- Ruiz-Castillo, P., Blackmond, D. G., Buchwald, S. L. Rational ligand design for the arylation of hindered primary amines guided by reaction progress kinetic analysis Journal of the American Chemical Society 2015 137:3085-3092 DOI:10.1021/ja512903g PMID:25651374 PMCID:PMC4379963
- Gherase, D., Conroy, D., Matar, O. K., Blackmond, D. G. Experimental and theoretical study of the emergence of single chirality in attrition-enhanced deracemization Crystal Growth and Design 2014 14:928-937 DOI:10.1021/cg401072d
- O'Brien, A. G., Maruyama, A., Inokuma, Y., Fujita, M., Baran, P. S., Blackmond, D. G. Radical C-H functionalization of heteroarenes under electrochemical control Angewandte Chemie-International Edition 2014 53:11868-11871 DOI:10.1002/anie.201407948 PMID:25209429 PMCID:PMC4214156
- Bures, J., Dingwall, P., Armstrong, A., Blackmond, D. G. Rationalization of an unusual solvent-induced inversion of enantiomeric excess in organocatalytic selenylation of aldehydes Angewandte Chemie-International Edition 2014 53:8700-8704 DOI:10.1002/anie.201404327 PMID:25044727
- Ji, Y., Blackmond, D. G. The role of reversibility in the enantioselective conjugate addition of alpha,alpha-disubstituted aldehydes to nitro-olefins catalyzed by primary amine thioureas Catalysis Science & Technology 2014 4:3505-3509 DOI:10.1039/c4cy00648h
- Hein, J. E., Gherase, D., Blackmond, D. G. Chemical and physical models for the emergence of biological homochirality Topics in Current Chemistry 2013 333:83-108 DOI:10.1007/128_2012_397 PMID:23271377
- Baxter, R. D., Blackmond, D. G. In situ kinetic studies of the trifluoromethylation of caffeine with Zn(SO2CF3)(2) Tetrahedron 2013 69:5604-5608 DOI:10.1016/j.tet.2013.04.007
- O'Hara, F., Blackmond, D. G., Baran, P. S. Radical-based regioselective C-H functionalization of electron-deficient heteroarenes: scope, tunability, and predictability Journal of the American Chemical Society 2013 135:12122-12134 DOI:10.1021/ja406223k PMID:23859263 PMCID:PMC3776592
- Bures, J., Armstrong, A., Blackmond, D. G. The interplay of thermodynamics and kinetics in dictating organocatalytic reactivity and selectivity Pure and Applied Chemistry 2013 85:1919-1934 DOI:10.1351/pac-con-13-01-14
- Fujiwara, Y., Dixon, J. A., Rodriguez, R. A., Baxter, R. D., Dixon, D. D., Collins, M. R., Blackmond, D. G., Baran, P. S. A new reagent for direct difluoromethylation Journal of the American Chemical Society 2012 134:1494-1497 DOI:10.1021/ja211422g PMID:22229949 PMCID:PMC3269891
- Bures, J., Armstrong, A., Blackmond, D. G. Curtin-Hammett paradigm for stereocontrol in organocatalysis by diarylprolinol ether catalysts Journal of the American Chemical Society 2012 134:6741-6750 DOI:10.1021/ja300415t PMID:22452319
- Bures, J., Armstrong, A., Blackmond, D. G. Kinetic correlation between aldehyde/enamine stereoisomers in reactions between aldehydes with alpha-stereocenters and chiral pyrrolidine-based catalysts Chemical Science 2012 3:1273-1277 DOI:10.1039/c2sc01082h
- Baxter, R. D., Sale, D., Engle, K. M., Yu, J. Q., Blackmond, D. G. Mechanistic rationalization of unusual kinetics in Pd-catalyzed C-H olefination Journal of the American Chemical Society 2012 134:4600-4606 DOI:10.1021/ja207634t PMID:22324814
- Gehring, T., Quaranta, M., Odell, B., Blackmond, D. G., Brown, J. M. Observation of a transient intermediate in Soai's asymmetric autocatalysis: Insights from 1H NMR turnover in real time Angewandte Chemie-International Edition 2012 51:9539-9542 DOI:10.1002/anie.201203398 PMID:22936384
- Hein, J. E., Blackmond, D. G. On the origin of single chirality of amino acids and sugars in biogenesis Accounts of Chemical Research 2012 45:2045-2054 DOI:10.1021/ar200316n PMID:22353168
- Hein, J. E., Cao, B. H., Viedma, C., Kellogg, R. M., Blackmond, D. G. Pasteur's tweezers revisited: on the mechanism of attrition-enhanced deracemization and resolution of chiral conglomerate solids Journal of the American Chemical Society 2012 134:12629-12636 DOI:10.1021/ja303566g PMID:22779695
- Hein, J. E., Tse, E., Blackmond, D. G. A route to enantiopure RNA precursors from nearly racemic starting materials Nature Chemistry 2011 3:704-706 DOI:10.1038/nchem.1108 PMID:21860459
- Hein, J. E., Bures, J., Lam, Y. H., Hughes, M., Houk, K. N., Armstrong, A., Blackmond, D. G. Enamine carboxylates as stereodetermining intermediates in prolinate catalysis Organic Letters 2011 13:5644-5647 DOI:10.1021/ol2023533 PMID:21958394
- Ji, Y. N., Brueckl, T., Baxter, R. D., Fujiwara, Y., Seiple, I. B., Su, S., Blackmond, D. G., Baran, P. S. Innate C-H trifluoromethylation of heterocycles Proceedings of the National Academy of Sciences of the United States of America 2011 108:14411-14415 DOI:10.1073/pnas.1109059108 PMID:21844378 PMCID:PMC3167544
- Hein, J. E., Armstrong, A., Blackmond, D. G. Kinetic profiling of prolinate-catalyzed alpha-amination of aldehydes Organic Letters 2011 13:4300-4303 DOI:10.1021/ol201639z PMID:21761822
- Bures, J., Armstrong, A., Blackmond, D. G. Mechanistic rationalization of organocatalyzed conjugate addition of linear aldehydes to nitro-olefins Journal of the American Chemical Society 2011 133:8822-8825 DOI:10.1021/ja203660r PMID:21568340
- Ferretti, A. C., Brennan, C., Blackmond, D. G. Reservoir catalysis: rationalization of anomalous reaction orders in Pd-catalyzed amination of aryl halides Inorganica Chimica Acta 2011 369:292-295 DOI:10.1016/j.ica.2011.01.018
- Blackmond, D. G. The origin of biological homochirality Philosophical Transactions of the Royal Society B-Biological Sciences 2011 366:2878-2884 DOI:10.1098/rstb.2011.0130 PMID:21930578 PMCID:PMC3158912
- Blackmond, D. G. Kinetic aspects of non-linear effects in asymmetric synthesis, catalysis, and autocatalysis Tetrahedron-Asymmetry 2010 21:1630-1634 DOI:10.1016/j.tetasy.2010.03.034
- Viedma, C., Verkuijl, B. J. V., Ortiz, J. E., de Torres, T., Kellogg, R. M., Blackmond, D. G. Solution-phase racemization in the presence of an enantiopure solid phase Chemistry-a European Journal 2010 16:4932-4937 DOI:10.1002/chem.200902983 PMID:20358554
- Valera, F. E., Quaranta, M., Moran, A., Blacker, J., Armstrong, A., Cabral, J. T., Blackmond, D. G. The flow's the thing ... Or is it? Assessing the merits of homogeneous reactions in flask and flow Angewandte Chemie-International Edition 2010 49:2478-2485 DOI:10.1002/anie.200906095 PMID:20187051
- Blackmond, D. G. The origin of biological homochirality Cold Spring Harbor Perspectives in Biology 2010 2:a002147 DOI:10.1101/cshperspect.a002147 PMID:20452962 PMCID:PMC2857173
- Quaranta, M., Gehring, T., Odell, B., Brown, J. M., Blackmond, D. G. Unusual inverse temperature dependence on reaction rate in the asymmetric autocatalytic alkylation of pyrimidyl aldehydes Journal of the American Chemical Society 2010 132:15104-15107 DOI:10.1021/ja103204w PMID:20942400
- Blackmond, D. G., Moran, A., Hughes, M., Armstrong, A. Unusual reversal of enantioselectivity in the proline-mediated alpha-amination of aldehydes induced by tertiary amine additives Journal of the American Chemical Society 2010 132:7598-7899 DOI:10.1021/ja102718x PMID:20465280
- Blackmond, D. G. "If pigs could fly" chemistry: A tutorial on the principle of microscopic reversibility Angewandte Chemie-International Edition 2009 48:2648-2654 DOI:10.1002/anie.200804566 PMID:19117002
- Zotova, N., Moran, A., Armstrong, A., Blackmond, D. G. A coherent mechanistic rationale for additive effects and autoinductive behaviour in proline-mediated reactions Advanced Synthesis & Catalysis 2009 351:2765-2769 DOI:10.1002/adsc.200900665
- Blackmond, D. G. An examination of the role of autocatalytic cycles in the chemistry of proposed primordial reactions Angewandte Chemie-International Edition 2009 48:386-390 DOI:10.1002/anie.200804565 PMID:19053125
- Blackmond, D. G. Challenging the concept of "recycling" as a mechanism for the evolution of homochirality in chemical reactions Chirality 2009 21:359-362 DOI:10.1002/chir.20592 PMID:18570293
- Zotova, N., Broadbelt, L. J., Armstrong, A., Blackmond, D. G. Kinetic and mechanistic studies of proline-mediated direct intermolecular aldol reactions Bioorganic & Medicinal Chemistry Letters 2009 19:3934-3937 DOI:10.1016/j.bmcl.2009.03.112 PMID:19362473
- Izumi, T., Blackmond, D. G. The double solubility rule holds for racemizing enantiomers Chemistry-a European Journal 2009 15:3065-3068 DOI:10.1002/chem.200801847 PMID:19222072
- Noorduin, W. L., Izumi, T., Millemaggi, A., Leeman, M., Meekes, H., Van Enckevort, W. J. P., Kellogg, R. M., Kaptein, B., Vlieg, E., Blackmond, D. G. Emergence of a single solid chiral state from a nearly racemic amino acid derivative Journal of the American Chemical Society 2008 130:1158-1159 DOI:10.1021/ja7106349 PMID:18173274
- Viedma, C., Ortiz, J. E., de Torres, T., Izumi, T., Blackmond, D. G. Evolution of solid phase homochirality for a proteinogenic amino acid Journal of the American Chemical Society 2008 130:15274-15275 DOI:10.1021/ja8074506 PMID:18954052
- Ferretti, A. C., Mathew, J. S., Ashworth, I., Purdy, M., Brennan, C., Blackmond, D. G. Mechanistic inferences derived from competitive catalytic reactions: Pd(binap)-catalyzed amination of aryl halides Advanced Synthesis & Catalysis 2008 350:1007-1012 DOI:10.1002/adsc.200800006
- Blackmond, D. G., Matar, O. K. Re-examination of reversibility in reaction models for the spontaneous emergence of homochirality Journal of Physical Chemistry B 2008 112:5098-5104 DOI:10.1021/jp7118586 PMID:18370430
- Blackmond, D. G. Response to "comment on 'a re-examination of reversibility in reaction models for the spontaneous emergence of homochirality'" Journal of Physical Chemistry B 2008 112:9553-9555 DOI:10.1021/jp8040378
- Blackmond, D. G., Klussmann, M. Investigating the evolution of biomolecular homochirality AIChE Journal 2007 53:2-8 DOI:10.1002/aic.11024
- Blackmond, D. G. Response to "Comments on a possible transition to solid-phase homochirality" Chemistry-a European Journal 2007 13:10306-10311 DOI:10.1002/chem.200701568
- Blackmond, D. G. "Chiral amnesia" as a driving force for solid-phase homochirality Chemistry-a European Journal 2007 13:3290-3295 DOI:10.1002/chem.200601463 PMID:17366493
- Zotova, N., Franzke, A., Armstrong, A., Blackmond, D. G. Clarification of the role of water in proline-mediated aldol reactions Journal of the American Chemical Society 2007 129:15100-15101 DOI:10.1021/ja0738881 PMID:18001021
- Phua, P. H., Mathew, S. P., White, A. J. P., de Vries, J. G., Blackmond, D. G., Hii, K. K. Elucidating the mechanism of the asymmetric aza-Michael reaction Chemistry-a European Journal 2007 13:4602-4613 DOI:10.1002/chem.200601706 PMID:17352437
- Klussmann, M., Izumi, T., White, A. J. P., Armstrong, A., Blackmond, D. G. Emergence of solution-phase homochirality via crystal engineering of amino acids Journal of the American Chemical Society 2007 129:7657-7660 DOI:10.1021/ja0708870 PMID:17530759
- Ferretti, A. C., Mathew, J. S., Blackmond, D. G. Reaction calorimetry as a tool for understanding reaction mechanisms: application to Pd-catalyzed reactions Industrial & Engineering Chemistry Research 2007 46:8584-8589 DOI:10.1021/ie070050d
- Blackmond, D. G., Klussmann, M. Spoilt for choice: Assessing phase behavior models for the evolution of homochirality Chemical Communications 2007 3990-3996 DOI:10.1039/b709314b PMID:17912393
- Blackmond, D. G., Armstrong, A., Coombe, V., Wells, A. Water in organocatalytic processes: Debunking the myths Angewandte Chemie-International Edition 2007 46:3798-3800 DOI:10.1002/anie.200604952 PMID:17361975
- Mathew, S. P., Klussmann, M., Iwamura, H., Wells, D. H., Armstrong, A., Blackmond, D. G. A mechanistic rationalization of unusual kinetic behavior in proline-mediated C-O and C-N bond-forming reactions Chemical Communications 2006 4291-4293 DOI:10.1039/b609926b PMID:17047844
- Blackmond, D. G., Schultz, T., Mathew, J. S., Loew, C., Rosner, T., Pfaltz, A. Comprehensive kinetic screening of palladium catalysts for heck reactions Synlett 2006 3135-3139 DOI:10.1055/s-2006-951514
- Mathew, J. S., Klussmann, M., Iwamura, H., Valera, F., Futran, A., Emanuelsson, E. A. C., Blackmond, D. G. Investigations of Pd-catalyzed ArX coupling reactions informed by reaction progress kinetic analysis Journal of Organic Chemistry 2006 71:4711-4722 DOI:10.1021/jo052409i PMID:16776495
- Klussmann, M., Mathew, S. R., Iwamura, H., Wells, D. H., Armstrong, A., Blackmond, D. G. Kinetic rationalization of nonlinear effects in asymmetric catalysis based on phase behavior Angewandte Chemie-International Edition 2006 45:7989-7992 DOI:10.1002/anie.200602521 PMID:17061299
- Blackmond, D. G., Ropic, M., Stefinovic, M. Kinetic studies of the asymmetric transfer hydrogenation of imines with formic acid catalyzed by Rh-diamine catalysts Organic Process Research & Development 2006 10:457-463 DOI:10.1021/op060033k
- Blackmond, D. G., Hodnett, N. S., Lloyd-Jones, G. C. Mechanistic implications of pseudo zero order kinetics in kinetic resolutions Journal of the American Chemical Society 2006 128:7450-7451 DOI:10.1021/ja062173f PMID:16756293
- Blackmond, D. G. Mechanistic study of the soai autocatalytic reaction informed by kinetic analysis Tetrahedron-Asymmetry 2006 17:584-589 DOI:10.1016/j.tetasy.2006.01.012
- Klussmann, M., White, A. J. R., Armstrong, A., Blackmond, D. G. Rationalization and prediction of solution enantiomeric excess in ternary phase systems Angewandte Chemie-International Edition 2006 45:7985-7989 DOI:10.1002/anie.200602520 PMID:16986192
- Shekhar, S., Ryberg, P., Hartwig, J. F., Mathew, J. S., Blackmond, D. G., Strieter, E. R., Buchwald, S. L. Reevaluation of the mechanism of the amination of aryl halides catalyzed by BINAP-ligated palladium complexes Journal of the American Chemical Society 2006 128:3584-3591 DOI:10.1021/ja045533c PMID:16536531
- Klussmann, M., Iwamura, H., Mathew, S. P., Wells, D. H., Pandya, U., Armstrong, A., Blackmond, D. G. Thermodynamic control of asymmetric amplification in amino acid catalysis Nature 2006 441:621-623 DOI:10.1038/nature04780 PMID:16738656
- Mathew, S. P., Gunathilagan, S., Roberts, S. M., Blackmond, D. G. Mechanistic insights from reaction progress kinetic analysis of the polypeptide-catalyzed epoxidation of chalcone Organic Letters 2005 7:4847-4850 DOI:10.1021/ol051708r PMID:16235904
- Blackmond, D. G. Reaction progress kinetic analysis: a powerful methodology for mechanistic studies of complex catalytic reactions Angewandte Chemie-International Edition 2005 44:4302-4320 DOI:10.1002/anie.200462544 PMID:15997457
- Strieter, E. R., Blackmond, D. G., Buchwald, S. L. The role of chelating diamine ligands in the goldberg reaction: a kinetic study on the copper-catalyzed amidation of aryl iodides Journal of the American Chemical Society 2005 127:4120-4121 DOI:10.1021/ja050120c PMID:15783164
- Arseniyadis, S., Subhash, P. V., Valleix, A., Mathew, S. P., Blackmond, D. G., Wagner, A., Mioskowski, C. Tuning the enantioselective N-acetylation of racemic amines: A spectacular salt effect Journal of the American Chemical Society 2005 127:6138-6139 DOI:10.1021/ja051302+ PMID:15853296
- Reetz, M. T., Meiswinkel, A., Mehler, G., Angermund, K., Graf, M., Thiel, W., Mynott, R., Blackmond, D. G. Why are BINOL-based monophosphites such efficient ligands in Rh-catalyzed asymmetric olefin hydrogenation? Journal of the American Chemical Society 2005 127:10305-10313 DOI:10.1021/ja052025+ PMID:16028942
- Mathew, S. P., Iwamura, H., Blackmond, D. G. Amplification of enantiomeric excess in a proline-mediated reaction Angewandte Chemie-International Edition 2004 43:3317-3321 DOI:10.1002/anie.200453997 PMID:15213963
- Blackmond, D. G. Asymmetric autocatalysis and its implications for the origin of homochirality Proceedings of the National Academy of Sciences of the United States of America 2004 101:5732-5736 DOI:10.1073/pnas.0308363101 PMID:15067112 PMCID:PMC395976
- Iwamura, H., Mathew, S. P., Blackmond, D. G. In situ catalyst improvement in the proline-mediated alpha-amination of aldehydes Journal of the American Chemical Society 2004 126:11770-11771 DOI:10.1021/ja046258x PMID:15382893
- LeBars, J., Dini, S., Hawkins, J. M., Blackmond, D. G. Mechanistic insights into anomalous kinetic behaviour in the hydrogenation of a substituted nitrobenzene Advanced Synthesis & Catalysis 2004 346:943-946 DOI:10.1002/adsc.200303202
- Nielsen, L. P. C., Stevenson, C. P., Blackmond, D. G., Jacobsen, E. N. Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides Journal of the American Chemical Society 2004 126:1360-1362 DOI:10.1021/ja038590z PMID:14759192
- Buono, F. G., Iwamura, H., Blackmond, D. G. Physical and chemical rationalization for asymmetric amplification in autocatalytic reactions Angewandte Chemie-International Edition 2004 43:2099-2103 DOI:10.1002/anie.200353086 PMID:15083455
- Iwamura, H., Wells, D. H., Mathew, S. P., Klussmann, M., Armstrong, A., Blackmond, D. G. Probing the active catalyst in product-accelerated proline-mediated reactions Journal of the American Chemical Society 2004 126:16312-16313 DOI:10.1021/ja0444177 PMID:15600319
- Richards, S., Ropic, M., Blackmond, D., Walmsley, A. Quantitative determination of the catalysed asymmetric transfer hydrogenation of 1-methyl-6,7-dimethoxy-3,4-dihydroisoquinoline using in situ FTIR and multivariate curve resolution Analytica Chimica Acta 2004 519:1-9 DOI:10.1016/j.aca.2004.05.021
- Strieter, E. R., Blackmond, D. G., Buchwald, S. L. Insights into the origin of high activity and stability of catalysts derived from bulky, electron-rich monophosphinobiaryl ligands in the Pd-catalyzed C-N bond formation Journal of the American Chemical Society 2003 125:13978-13980 DOI:10.1021/ja037932y PMID:14611232
- Buono, F. G., Blackmond, D. G. Kinetic evidence for a tetrameric transition state in the asymmetric autocatalytic alkylation of pyrimidyl aldehydes Journal of the American Chemical Society 2003 125:8978-8979 DOI:10.1021/ja034705n PMID:15369330
- Blackmond, D. G. Description of the condition for asymmetric amplification in autocatalytic reactions Advanced Synthesis & Catalysis 2002 344:156-158 DOI:10.1002/1615-4169(200202)344:2<156::aid-adsc156>3.0.co;2-1
- Singh, U. K., Strieter, E. R., Blackmond, D. G., Buchwald, S. L. Mechanistic insights into the Pd(BINAP)-catalyzed amination of aryl bromides: kinetic studies under synthetically relevant conditions Journal of the American Chemical Society 2002 124:14104-14114 DOI:10.1021/ja026885r PMID:12440909
- Buono, F., Walsh, P. J., Blackmond, D. G. Rationalization of anomalous nonlinear effects in the alkylation of substituted benzaldehydes Journal of the American Chemical Society 2002 124:13652-13653 DOI:10.1021/ja027406r PMID:12431076
- Blackmond, D. G. Requiem for the reaction rate equation? Catalysis Letters 2002 83:133-136 DOI:10.1023/a:1021041925818
- Le Bars, J., Haussner, T., Lang, J., Pfaltz, A., Blackmond, D. G. A scale-transparent reaction calorimetric assay for rapid catalyst selection Advanced Synthesis & Catalysis 2001 343:207-214 DOI:10.1002/1615-4169(20010226)343:2<207::aid-adsc207>3.3.co;2-v
- Blackmond, D. G. Kinetic resolution using enantioimpure catalysts: mechanistic considerations of complex rate laws Journal of the American Chemical Society 2001 123:545-553 DOI:10.1021/ja002562o PMID:11456566
- Rosner, T., Le Bars, J., Pfaltz, A., Blackmond, D. G. Kinetic studies of heck coupling reactions using palladacycle catalysts: Experimental and kinetic modeling of the role of dimer species Journal of the American Chemical Society 2001 123:1848-1855 DOI:10.1021/ja00319le PMID:11456804
- Rosner, T., Pfaltz, A., Blackmond, D. G. Observation of unusual kinetics in Heck reactions of aryl halides: the role of non-steady-state catalyst concentration Journal of the American Chemical Society 2001 123:4621-4622 DOI:10.1021/ja005872f PMID:11457257
- Blackmond, D. G., McMillan, C. R., Ramdeehul, S., Schorm, A., Brown, J. M. Origins of asymmetric amplification in autocatalytic alkylzinc additions Journal of the American Chemical Society 2001 123:10103-10104 DOI:10.1021/ja0165133 PMID:11592892
- Blackmond, D. G., Lightfoot, A., Pfaltz, A., Rosner, T., Schnider, P., Zimmerman, N. Enantioselective hydrogenation of olefins with phosphinooxazoline-iridium catalysts Chirality 2000 12:442-449 DOI:10.1002/(sici)1520-636x(2000)12:5/6<442::aid-chir25>3.0.co;2-f PMID:10824167
- Blackmond, D. G. Kinetic aspects of nonlinear effects in asymmetric catalysis Accounts of Chemical Research 2000 33:402-411 DOI:10.1021/ar990083s PMID:10891058
- Rosner, T., Sears, P. J., Nugent, W. A., Blackmond, D. G. Kinetic investigations of product inhibition in the amino alcohol-catalyzed asymmetric alkylation of benzaldehyde with diethylzinc Organic Letters 2000 2:2511-2513 DOI:10.1021/ol006181r PMID:10956534
- Le Bars, J., Specht, U., Bradley, J. S., Blackmond, D. G. A catalytic probe of the surface of colloidal palladium particles using heck coupling reactions Langmuir 1999 15:7621-7625 DOI:10.1021/la990144v
- Blackmond, D. G., Rosner, T., Pfaltz, A. Comprehensive kinetic screening of catalysts using reaction calorimetry Organic Process Research & Development 1999 3:275-280 DOI:10.1021/op990024u
- Blackmond, D. G., Rosner, T., Neugebauer, T., Reetz, M. T. Kinetic influences on enantioselectivity for non-diastereopure catalyst mixtures Angewandte Chemie-International Edition 1999 38:2196-2199 DOI:10.1002/(sici)1521-3773(19990802)38:15<2196::aid-anie2196>3.0.co;2-9 PMID:10425479
- Blackmond, D. G. Comments on "Nature of initial transient period during enantioselective hydrogenation on Pt and Pd" by T. Mallat, Z. Bodnar, B. Minder, K. Borszeky, and A. Baiker Journal of Catalysis 1998 176:267-270 DOI:10.1006/jcat.1998.2080
- Blackmond, D. G., Leitner, W. Fine chemicals catalysis - Part II - Preface Topics in Catalysis 1998 5:U9-U10
- Siedlaczek, G., Schwickardi, M., Kolb, U., Bogdanovic, B., Blackmond, D. G. Diastereoselective reductive amination reactions using novel metal-carbon catalysts prepared front inorganic grignard reagents Catalysis Letters 1998 55:67-72 DOI:10.1023/a:1019026711011
- Blackmond, D. G. Kinetic implications of nonlinear effects in asymmetric synthesis Journal of the American Chemical Society 1998 120:13349-13353 DOI:10.1021/ja982448u
- Bohnen, F. M., Gamez, A., Blackmond, D. G. On the implications of hemiketal formation during ethyl pyruvate hydrogenation in alcohol solvents Journal of Catalysis 1998 179:335-338 DOI:10.1006/jcat.1998.2247
- Blackmond, D. G., Leitner, W. Fine chemicals catalysis, part I - Preface Topics in Catalysis 1997 4:U9-U10
- Wang, J., LeBlond, C., Orella, C. F., Sun, Y. K., Bradley, J. S., Blackmond, D. G. Modeling of kinetically coupled selective hydrogenation reactions: Kinetic rationalization of pressure effects on enantioselectivity Studies in Surface Science and Catalysis 1997 108:183-190
- Wang, J., LeBlond, C., Landau, R. N., Laquidara, J., Sowa, J. R., Blackmond, D. G. Kinetic influences on enantioselectivity in asymmetric catalytic hydrogenation Journal of Molecular Catalysis A-Chemical 1997 115:495-502 DOI:10.1016/s1381-1169(96)00353-6
- Wang, J., LeBlond, C., Reamer, R. A., Laquidara, J., Sowa, J. R., Blackmond, D. G. Kinetic influences on enantioselectivity in asymmetric catalytic hydrogenation Journal of Organometallic Chemistry 1997 548:65-72 DOI:10.1016/s0022-328x(97)00165-4
- Blackmond, D. G. Mathematical models of nonlinear effects in asymmetric catalysis: new insights based on the role of reaction rate Journal of the American Chemical Society 1997 119:12934-12939 DOI:10.1021/ja973049m
- Sun, Y. K., Landau, R. N., Wang, J., LeBlond, C., Blackmond, D. G. A re-examination of pressure effects on enantioselectivity in asymmetric catalytic hydrogenation Journal of the American Chemical Society 1996 118:1348-1353 DOI:10.1021/ja952988g
- Sun, Y. K., Wang, J., Leblond, C., Landau, R. N., Blackmond, D. G. Asymmetric hydrogenation of ethyl pyruvate: Diffusion effects on enantioselectivity Journal of Catalysis 1996 161:759-765 DOI:10.1006/jcat.1996.0238
- Wang, J., Sun, Y. K., Leblond, C., Landau, R. N., Blackmond, D. G. Asymmetric hydrogenation of ethyl pyruvate: Relationship between conversion and enantioselectivity Journal of Catalysis 1996 161:752-758 DOI:10.1006/jcat.1996.0237
- LeBlond, C., Wang, J., Larsen, R. D., Orella, C. J., Forman, A. L., Landau, R. N., Laquidara, J., Sowa, J. R., Blackmond, D. G., Sun, Y. K. Reaction calorimetry as an in-situ kinetic tool for characterizing complex reactions Thermochimica Acta 1996 289:189-207 DOI:10.1016/s0040-6031(96)03072-9
- Landau, R. N., Singh, U., Gortsema, F., Sun, Y. K., Gomolka, S. C., Lam, T., Futran, M., Blackmond, D. G. A reaction calorimetric investigation of the hydrogenation of a substituted pyrazine Journal of Catalysis 1995 157:201-208 DOI:10.1006/jcat.1995.1280
- Wang, J., Oukaci, R., Wender, I., Blackmond, D. G. Alcohol synthesis from co/h-2 over co/cu/zno/al2o3 - in-situ addition of ch3no2 Journal of Catalysis 1995 153:100-107 DOI:10.1006/jcat.1995.1112
- Singh, U. K., Landau, R. N., Sun, Y. K., Leblond, C., Blackmond, D. G., Tanielyan, S. K., Augustine, R. L. Enantioselective catalysis - influence of conversion and bulk diffusion limitations on selectivity in the hydrogenation of ethyl pyruvate Journal of Catalysis 1995 154:91-97 DOI:10.1006/jcat.1995.1150
- Sun, Y. K., LeBlond, C., Wang, J., Blackmond, D. G. Observation of a RuCl2((S)-((-))-tol-binap) (2).N(C2H5)(3)-catalyzed isomerization-hydrogenation network Journal of the American Chemical Society 1995 117:12647-12648 DOI:10.1021/ja00155a034
- Blackmond, D. G. 15th Conference on Catalysis of Organic Reactions, 2–5 May, 1994, Phoenix, AZ Applied Catalysis A-General 1994 115:N7-N8 DOI:10.1016/0926-860x(94)80394-3
- Blackmond, D. CHICAT - Chiral reactions in heterogeneous catalysis, Brussels, Belgium, October 25-26, 1993 Applied Catalysis A-General 1994 107:N23-N25 DOI:10.1016/0926-860x(94)85174-3
- Landau, R. N., Blackmond, D. G., Tung, H. H. Calorimetric investigation of an exothermic reaction: kinetic and heat-flow modeling Industrial & Engineering Chemistry Research 1994 33:814-820 DOI:10.1021/ie00028a005
- Landau, R. N., Blackmond, D. G. Scale-up heat-transfer based on reaction calorimetry Chemical Engineering Progress 1994 90:43-48
- Holmlid, L., Engvall, K., Aman, C., Menon, P. G., Haller, G. L., Kochloefl, K., Pernicone, N., Baranski, A., Blackmond, D. G., Cameron, C., Aika, K., Fisher, G. B. A new approach to loss of alkali promoter from industrial catalysts - importance of excited-states of alkali Studies in Surface Science and Catalysis 1993 75:795-807
- Badani, M. V., Eshelman, L. M., Delgass, W. N., Prins, R., Vannice, M. A., Suresh, D., Conner, W. C., Ponec, V., Blackmond, D. G., Homs, N., Bhasin, M. M. Acetonitrile synthesis from co, h2 and nh3 over fe/c and k,fe/c Studies in Surface Science and Catalysis 1993 75:1223-1234
- Choudary, B. M., Rani, S. S., Rao, Y. V. S., Arntz, D., Kiricsi, I., Simons, K., Blackmond, D. G., Ratnasamy, P., Johnson, P., Holderich, W. An improved asymmetric oxidation of sulfides to sulfoxides by titanium pillared montmorillonite - the 1st example in heterogeneous catalysis Studies in Surface Science and Catalysis 1993 75:1247-1255
- Schroder, U., Cider, L., Schoon, N. H., Baltanas, M. A., Blackmond, D. G., Datye, A. K., Conner, W. C., Hightower, J. W., Guo, X. X., Wang, D. An in-situ radioactive-tracer technique for studying adsorption-desorption dynamics on a working catalyst Studies in Surface Science and Catalysis 1993 75:643-657
- Waghray, A., Blackmond, D. G. Infrared spectroscopic studies of the adsorption and reaction of 3-methyl-2-butenal over alkali-promoted ru/sio2 catalysts Journal of Physical Chemistry 1993 97:6002-6006 DOI:10.1021/j100124a036
- Murrell, L. L., Tauster, S. J., Anderson, D. R., Bozonverduraz, F., Woo, S. I., Conner, W. C., Conesa, J. C., Blackmond, D. G., Ichikawa, M., Bartholomew, C. H. Laser raman characterization of surface phase precious-metal oxides formed on ceo2 micro domains generated within an alumina host by sol synthesis Studies in Surface Science and Catalysis 1993 75:681-690
- Marinelli, Tblw, Vleeming, J. H., Ponec, V., Wang, D., Blackmond, D. G., Arntz, D., Jannes, G., Kunimori, K., Rochester, C. H. Reactions of multifunctional organic-compounds - hydrogenation of acrolein on modified pt-catalysts Studies in Surface Science and Catalysis 1993 75:1211-1222
- Waghray, A., Oukaci, R., Blackmond, D. G. Selective hydrogenation of alpha,beta-unsaturated aldehydes over supported ru Studies in Surface Science and Catalysis 1993 75:2479-2482
- Balakos, M. W., Chuang, S. S. C., Krishnamurthy, R., Srinivas, G., Johnston, P., Blackmond, D. G., Jackson, S. D., Joyner, R. W. The selective synthesis of c2+ oxygenates from syngas related reactions over ni-based and rh-based catalysts Studies in Surface Science and Catalysis 1993 75:1467-1478
- Lin, S. D., Vannice, M. A., Herrmann, J. M., Wang, D., Apestequia, C., Duprez, D., Figueras, F., Conner, W. C., Kiperman, S. L., Hall, W. K., Blackmond, D. G., Grunert, W., et al. Toluene hydrogenation over supported platinum catalysts Studies in Surface Science and Catalysis 1993 75:861-874
- Brusky, P., Blackmond, D. G. Meeting Reports. 14th International Conference on the Catalysis of Organic Reactions, Albuquerque, New Mexico, 27-29 April, 1992 Applied Catalysis A-General 1992 87:N13-N14 DOI:10.1016/0926-860X(92)80191-E
- Waghray, A., Oukaci, R., Blackmond, D. G. Diffusion effects in the hydrogenation of 3-methyl crotonaldehyde over zeolite-supported ru Catalysis Letters 1992 14:115-122 DOI:10.1007/bf00764225
- Waghray, A., Wang, J., Oukaci, R., Blackmond, D. G. Influence of alkali promoters in the selective hydrogenation of 3-methyl-2-butenal over ru/sio2 catalysts Journal of Physical Chemistry 1992 96:5954-5959 DOI:10.1021/j100193a056
- Oukaci, R., Blackmond, D. G., Goodwin, J. G., Gallaher, G. R. Steady-state isotopic transient kinetic analysis investigation of CO—O(2) and CO—NO reactions over a commercial automotive catalyst ACS Symposium Series 1992 495:61-72 DOI:10.1021/bk-1992-0495.ch005
- Cavalcanti, F. A. P., Oukaci, R., Wender, I., Blackmond, D. G. CH3NO2 addition to co hydrogenation over a RU/KY catalyst Journal of Catalysis 1991 128:311-319 DOI:10.1016/0021-9517(91)90291-b
- Blackmond, D. G., Oukaci, R., Blanc, B., Gallezot, P. Geometric and electronic effects in the selective hydrogenation of alpha,beta-unsaturated aldehydes over zeolite-supported metals Journal of Catalysis 1991 131:401-411 DOI:10.1016/0021-9517(91)90275-9
- Cavalcanti, F. A. P., Qukaci, R., Wender, I., Blackmond, D. G. Nitroethane as a probe molecule for CO hydrogenation over RU/SIO2 Journal of Catalysis 1990 123:270-274 DOI:10.1016/0021-9517(90)90175-j
- Cavalcanti, F. A. P., Oukaci, R., Wender, I., Blackmond, D. G. Probe molecule studies of co hydrogenation over ru/sio2 Journal of Catalysis 1990 123:260-269 DOI:10.1016/0021-9517(90)90174-i
- Blackmond, D. G., Swid, K. P., Davis, M. E., Gallezot, P. The nature of Rh-CO interactions on SAPO-5-supported Rh Journal of Catalysis 1990 122:247-255 DOI:10.1016/0021-9517(90)90279-s
- Cavalcanti, F. A. P., Blackmond, D. G., Oukaci, R., Sayari, A., Erdemsenatalar, A., Wender, I. Insitu chemical trapping of CO/H-2 surface species Journal of Catalysis 1988 113:1-12 DOI:10.1016/0021-9517(88)90232-1
- Ciocco, M. V., Blackmond, D. G. Support and alkali promotion effects on the surface-chemistry of nickel silica catalysts Applied Catalysis 1988 44:105-116 DOI:10.1016/s0166-9834(00)80047-0
- Kesraoui, S., Oukaci, R., Blackmond, D. G. Adsorption and reaction of CO and H-2 on K-promoted Rh/SIO2 catalysts Journal of Catalysis 1987 105:432-444 DOI:10.1016/0021-9517(87)90071-6
- Blackmond, D. G., Williams, J. A., Kesraoui, S., Blazewick, D. S. The effects of CS promotion on Rh/Al2O3 catalysts Journal of Catalysis 1986 101:496-504 DOI:10.1016/0021-9517(86)90276-9
- Blackmond, D. G., Ko, E. I. Carbon-monoxide adsorption as a chemical probe of supported nickel-catalysts - the role of carbonyl formation and support effects Journal of Catalysis 1985 94:343-352 DOI:10.1016/0021-9517(85)90199-x
- Blackmond, D. G., Ko, E. I. Structural sensitivity of H-2/CO adsorption on Ni/SiO2 catalysts Journal of Catalysis 1985 96:210-221 DOI:10.1016/0021-9517(85)90374-4
- Blackmond, D. G., Ko, E. I. Preparation and characterization of well-defined Ni/SiO2 catalysts Applied Catalysis 1984 13:49-68 DOI:10.1016/s0166-9834(00)83327-8
- Blackmond, D. G., Goodwin, J. G., Lester, J. E. Insitu fourier-transform infrared-spectroscopy study of hy cracking catalysts - coke formation and the nature of the active-sites Journal of Catalysis 1982 78:34-43 DOI:10.1016/0021-9517(82)90283-4
- Blackmond, D. G., Goodwin, J. G. The effect of hydrogen on the adsorption and reaction of 1-Hexene over HY cracking catalysts Journal of Catalysis 1982 78:247-252 DOI:10.1016/0021-9517(82)90304-9
- Blackmond, D. G., Goodwin, J. G. Zeolite support effects on CO-Ru interactions Journal of the Chemical Society-Chemical Communications 1981 125-126 DOI:10.1039/c39810000125
Research
research overview
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Kinetic Methodology. Blackmond has pioneered the development of Reaction Progress Kinetic Analysis (RPKA), a methodology combining highly accurate in-situ data collection with a rigorous mathematical analysis that permits rapid determination of concentration dependences of reactants. In contrast to the classical role of kinetics, in which measurements of concentration dependences most often are asked simply to corroborate a previously proposed mechanism, the Blackmond group’s approach is to employ kinetic studies at the outset of an investigation of ill-defined reaction network to suggest reaction mechanisms. This “kinetic-assisted mechanistic analysis” aids in the design of further supporting experiments including conventional mechanistic tools such as studies of isotope effects and spectroscopic studies for structural and compositional information. One of the most powerful aspects of the methodology is its ability to deconvolute rate processes occurring on the catalytic cycle from those occurring off the cycle. Prominent examples of the application of this methodology to quantitative understanding of complex organic reactions and reaction networks include asymmetric hydrogenation, asymmetric organocatalytic reactions, Pd-catalyzed C-C and C-N bond forming reactions, and transition-metal catalyzed competitive reactions including kinetic resolutions. Reaction Progress Kinetic Analysis finds important application in the pharmaceutical industry, where streamlining process R&D based on Blackmond’s kinetic analysis is becoming an industry-wide standard.
Nonlinear effects of catalyst enantiopurity. Experimental and theoretical studies in the Blackmond group have derived relationships between catalyst ee and reaction rate that complement the standard tool of studying product ee as a function of catalyst ee. Prof. Blackmond’s work provides a means of testing proposed models for nonlinear effects and expands the power of studies of nonlinear effects to serve as a meaningful mechanistic probe. The concepts developed in this work led Prof. Blackmond to consideration of what has been termed the “ultimate nonlinear effect”, that of the origin of biological homochirality. She carried out the first kinetic studies and developed the first kinetic model exploring the mechanism of asymmetric amplification in the Soai autocatalytic reaction. She continues investigations of this reaction, with current projects focusing on determining the nature of the transition state species in this reaction as well as probing spatiotemporal aspects of absolute asymmetric synthesis by carrying out autocatalysis in well-defined microfluidic reactor networks.
Biological homochirality and amino acid phase behavior. More recently Prof. Blackmond has expanded the range of models to rationalize the origin of biological homochirality from proposals based purely on chemical reactions to those based on physical phase behavior of chiral molecules as well as a combination of chemical and physical processes. She has demonstrated that highly enantioenriched solutions of amino acids can be produced from nearly racemic mixtures via solution-solid partitioning of the enantiomers. Reactions catalyzed by amino acids that are carried out in such systems show nonlinear product ee consistent with this highly enantioenriched solution composition. This concept was then greatly expanded in scope with the discovery that eutetic compositions could be “tuned” by judicious choice of additives that alter crystal structure and solubility. In sharp contrast to autocatalytic reaction models, which invoke “far-from-equilibrium” behavior, this eutectic model is a pure equilibrium treatment. This distinction has important implications for scenarios concerning the time course over which the evolution of homochirality may have developed.
Probing the phase behavior of amino acids in conjunction with solution racemization led to separate work showing how one hand of a chiral solid could be transformed completely into its enantiomorph from a nearly racemic mixture of the two. Because interconversion in solution allows an enantiomer that had been part of an L crystal to become part of a D crystal, this has been dubbed the “chiral amnesia” process.
Teaching
advisees
-
graduate advising relationship
- Hill, David, Ph.D. candidate, 2016 -
- Hawbaker, Neil A, Ph.D. candidate, 2013 - 2018
- Mower, Matthew, Ph.D. candidate, 2013 - 2018
Background
education and training
- Ph.D. in Chemical Engineering, Carnegie Mellon University 1984
- M.S. in Chemical Engineering, University of Pittsburgh 1981
- B.S. in Chemical Engineering, University of Pittsburgh 1980
awards and honors
- Distinguished Women in Chemistry or Chemical Engineering, conferred by The International Union of Pure and Applied Chemistry (IUPAC) , 2019
- Fellow of the American Academy of Arts and Sciences, conferred by American Academy of Arts & Sciences, 2016
- Chemical Pioneer Award, conferred by American Institute of Chemists, 2016
- Gabor A. Somorjai Award for Creative Research in Catalysis, conferred by American Chemical Society, 2016
- Simons Investigator, Collaboration on the Origins of Life, conferred by Simons Foundation, 2013
- Elected Member, conferred by National Academy of Engineering, 2013
- Physical Organic Chemistry Award, conferred by Royal Society of Chemistry, 2009
- Wolfson Research Merit Award, conferred by The Royal Society of London, 2007
- Arthur C. Cope Scholar Award, conferred by American Chemical Society, 2005
- Paul Rylander Award, conferred by Organic Reactions Catalysis Society, 2003
- Royal Society of Chemistry Award in Process Technology, conferred by Royal Society of Chemistry, 2002
- Paul H. Emmett Award in Fundamental Catalysis, conferred by North American Catalysis Society, 2001
- Max-Planck-Society Award for Outstanding Women Scientists, conferred by Max Planck Society for the Advancement of Science, 1998
- Presidential Young Investigator Award, conferred by National Science Foundation, 1985 - 1990
Contact
full name
- Donna Blackmond