BLACKMONDLAB
PUBLICATIONS
2019
Xiang, J.; Shang, M.; Kawamata, Y.; Lundberg, H.; Reisberg, S.H.; Chen, M.; Mykhailiuk, P.; Beutner, G.; Collins, M.R.; Davies, A.; Del Bel, M.; Gallego, G.M.; Spangler, J.E.; Starr, J.; Yang, S.; Blackmond, D.G.; Baran, P.S. Hindered dialkyl ether synthesis with electrogenerated carbocations. Nature 2019, 573 (7774), 398-402. PMID: 31501569.
Schmidt, O.P.; Dechert‐Schmitt, A.M.; Garnsey, M.R.; Wisniewska, H.M.; Blackmond, D.G. Kinetic analysis of catalytic organic reactions using a temperature scanning protocol. ChemCatChem 2019, 11 (16), 3808-3813. — Invited contribution for special issue “Women of Catalysis”
Hawbaker, N.A.; Blackmond, D.G. Energy threshold for chiral symmetry breaking in molecular self-replication. Nat Chem 2019, 11 (10), 957-962. PMID: 31548669.
Wisniewski, S.R.; Savage, S.A.; Romero, E.O.; Eastgate, M.D.; Tan, Y.; Simmons, E.M.; Plata, R.E.; Sowa, J.R., Jr.; Blackmond, D.G. Utilizing native directing groups: Mechanistic understanding of a direct arylation leads to formation of tetracyclic heterocycles via tandem intermolecular, intramolecular C-H activation. J Org Chem 2019, 84 (12), 7961-7970. PMID: 31117568.
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 Catal 2019, 9 (5), 4508-4515.
Blackmond, D.G. The origin of biological homochirality. Cold Spring Harb Perspect Biol 2019, 11 (3), a032540. PMID: 30824575.
2018
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 Catal 2018, 8 (10), 9537-9542. PMID: 30505624.
Hawbaker, N.A.; Blackmond, D.G. Rationalization of asymmetric amplification via autocatalysis triggered by isotopically chiral molecules. ACS Cent Sci 2018, 4 (6), 776-780. PMID: 29974074.
Mower, M.P.; Blackmond, D.G. In-situ monitoring of enantiomeric excess during a catalytic kinetic resolution. ACS Catal 2018, 8 (7), 5977-5982.
Wang, J.; Lundberg, H.; Asai, S.; Martín-Acosta, P.; Chen, J.S.; Brown, S.; Farrell, W.; Dushin, R.G.; O'Donnell, C.J.; Ratnayake, A.S.; Richardson, P.; Liu, Z.; Qin, T.; Blackmond, D.G.; Baran, P.S. Kinetically guided radical-based synthesis of C(sp(3))-C(sp(3)) linkages on DNA. Proc Natl Acad Sci USA 2018, 115 (28), E6404-E6410. PMID: 29946037.
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(sp3)–H Bond Arylation. ACS Catal 2018, 8 (2), 1528-1531.
2017
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. J Am Chem Soc 2017, 139 (51), 18500-18503. PMID: 29215885.
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.; Glace, A.W.; Freitag, A.; Sweeney, J.; Ji, Y.; Blackmond, D.G.; Eastgate, M.D.; Conlon, D.A. Preparation of the HIV attachment inhibitor BMS-663068. Part 7. Development of a regioselective Ullmann–Goldberg–Buchwald reaction. Org Process Res Dev 2017, 21 (8), 1156-1165.
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. J Am Chem Soc 2017, 139 (27), 9238-9245. PMID: 28605190.
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.; Grubbs, R.H.; Houk, K.N.; Stoltz, B.M. Potassium tert-butoxide-catalyzed dehydrogenative C-H silylation of heteroaromatics: A combined experimental and computational mechanistic study. J Am Chem Soc 2017, 139 (20), 6867-6879. PMID: 28403611.
Wagner, A.J.; Zubarev, D.Y.; Aspuru-Guzik, A.; Blackmond, D.G. Chiral sugars drive enantioenrichment in prebiotic amino acid synthesis. ACS Cent Sci 2017, 3 (4), 322-328. PMID: 28470050.
Gherase, D.; Hazen, R.M.; Krishnamurthy, R.; Blackmond, D.G. Mineral-induced enantioenrichment of tartaric acid. Synlett 2017, 28 (01), 89-92. — Cluster on Prebiotic Chemistry, invited submission
2016
Wagner, A.J.; Blackmond, D.G. The future of prebiotic chemistry. ACS Cent Sci 2016, 2 (11), 775-777. PMID: 27924306. — invited First Reactions Essay
Shi, Q.; Mower, M.P.; Blackmond, D.G.; Rebek, J., Jr. Water-soluble cavitands promote hydrolyses of long-chain diesters. Proc Natl Acad Sci USA 2016, 113 (33), 9199-203. PMID: 27482089.
Stich, M.; Ribó, J.M.; Blackmond, D.G.; Hochberg, D. Necessary conditions for the emergence of homochirality via autocatalytic self-replication. J Chem Phys 2016, 145 (7), 074111. PMID: 27544091.
Masseroni, D.; Mosca, S.; Mower, M.P.; Blackmond, D.G.; Rebek, J., Jr. Cavitands as reaction vessels and blocking groups for selective reactions in water. Angew Chem Int Ed Engl 2016, 55 (29), 8290-3. PMID: 27254667.
Burés, J.; Armstrong, A.; Blackmond, D.G. Explaining anomalies in enamine catalysis: "Downstream species" as a new paradigm for stereocontrol. Acc Chem Res 2016, 49 (2), 214-22. PMID: 26830669.
Elsila, J.E.; Aponte, J.C.; Blackmond, D.G.; Burton, A.S.; Dworkin, J.P.; Glavin, D.P. Meteoritic amino acids: Diversity in compositions reflects parent body histories. ACS Cent Sci 2016, 2 (6), 370-9. PMID: 27413780.
O'Brien, A.G.; Luca, O.R.; Baran, P.S.; Blackmond, D.G. In situ FTIR spectroscopic monitoring of electrochemically controlled organic reactions in a recycle reactor. React Chem Eng 2016, 1 (1), 90-95. PMID: 27069673.
Hawbaker, N.; Wittgrove, E.; Christensen, B.; Sach, N.; Blackmond, D.G. Dispersion in compartmentalized flow systems: Influence of flow patterns on reactivity. Org Process Res Dev 2016, 20 (2), 465-473.
2015
Baxter, R.D.; Liang, Y.; Hong, X.; Brown, T.A.; Zare, R.N.; Houk, K.N.; Baran, P.S.; Blackmond, D.G. Mechanistic insights into two-phase radical C-H arylations. ACS Cent Sci 2015, 1 (8), 456-462. PMID: 26640819.
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. J Am Chem Soc 2015, 137 (41), 13272-81. PMID: 26461028.
Blackmond, D.G. Kinetic profiling of catalytic organic reactions as a mechanistic tool. J Am Chem Soc 2015, 137 (34), 10852-66. PMID: 26285166. — invited Perspective article
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. J Am Chem Soc 2015, 137 (8), 3085-92. PMID: 25651374.
Mower, M.P.; Blackmond, D.G. Mechanistic rationalization of unusual sigmoidal kinetic profiles in the Machetti-De Sarlo cycloaddition reaction. J Am Chem Soc 2015, 137 (6), 2386-91. PMID: 25611219.
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. J Org Chem 2015, 80 (3), 1696-702. PMID: 25562708.
2014
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. Angew Chem Int Ed Engl 2014, 53 (44), 11868-71. PMID: 25209429. — Hot Paper
Burés, J.; Dingwall, P.; Armstrong, A.; Blackmond, D.G. Rationalization of an unusual solvent-induced inversion of enantiomeric excess in organocatalytic selenylation of aldehydes. Angew Chem Int Ed Engl 2014, 53 (33), 8700-4. PMID: 25044727.
Ji, Y.; Blackmond, D.G. The role of reversibility in the enantioselective conjugate addition of α,α-disubstituted aldehydes to nitro-olefins catalyzed by primary amine thioureas. Catal Sci Technol 2014, 4 (10), 3505-3509.
Gherase, D.; Conroy, D.; Matar, O.K.; Blackmond, D.G. Experimental and theoretical study of the emergence of single chirality in attrition-enhanced deracemization. Crystl Growth Des 2014, 14 (3), 928-937.
2013
O'Hara, F.; Blackmond, D.G.; Baran, P.S. Radical-based regioselective C-H functionalization of electron-deficient heteroarenes: scope, tunability, and predictability. J Am Chem Soc 2013, 135 (32), 12122-34. PMID: 23859263.
Burés, J.; Armstrong, A.; Blackmond, D.G. The interplay of thermodynamics and kinetics in dictating organocatalytic reactivity and selectivity. Pure Appl Chem 2013, 85 (10), 1919-1934.
Baxter, R.D.; Blackmond, D.G. In situ kinetic studies of the trifluoromethylation of caffeine with Zn(SO2CF3)2. Tetrahedron 2013, 69 (27), 5604-5608.
Hein, J.E.; Gherase, D.; Blackmond, D.G. Chemical and physical models for the emergence of biological homochirality. Top Curr Chem 2013, 333, 83-108. PMID: 23271377.
2012
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. J Am Chem Soc 2012, 134 (30), 12629-36. PMID: 22779695.
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. Angew Chem Int Ed Engl 2012, 51 (38), 9539-42. PMID: 22936384.
Burés, J.; Armstrong, A.; Blackmond, D.G. Curtin-Hammett paradigm for stereocontrol in organocatalysis by diarylprolinol ether catalysts. J Am Chem Soc 2012, 134 (15), 6741-50. PMID: 22452319.
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. J Am Chem Soc 2012, 134 (10), 4600-6. PMID: 22324814.
Hein, J.E.; Blackmond, D.G. On the origin of single chirality of amino acids and sugars in biogenesis. Acc Chem Res 2012, 45 (12), 2045-54. PMID: 22353168.
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. J Am Chem Soc 2012, 134 (3), 1494-7. PMID: 22229949.
Burés, J.; Armstrong, A.; Blackmond, D.G. Kinetic correlation between aldehyde/enamine stereoisomers in reactions between aldehydes with α-stereocenters and chiral pyrrolidine-based catalysts. Chem Sci 2012, 3 (4), 1273-1277.
2011
Hein, J.E.; Burés, J.; Lam, Y.H.; Hughes, M.; Houk, K.N.; Armstrong, A.; Blackmond, D.G. Enamine carboxylates as stereodetermining intermediates in prolinate catalysis. Org Lett 2011, 13 (20), 5644-7. PMID: 21958394.
Hein, J.E.; Tse, E.; Blackmond, D.G. A route to enantiopure RNA precursors from nearly racemic starting materials. Nat Chem 2011, 3 (9), 704-6. PMID: 21860459.
Hein, J.E.; Armstrong, A.; Blackmond, D.G. Kinetic profiling of prolinate-catalyzed α-amination of aldehydes. Org Lett 2011, 13 (16), 4300-3. PMID: 21761822.
Ji, Y.; Brueckl, T.; Baxter, R.D.; Fujiwara, Y.; Seiple, I.B.; Su, S.; Blackmond, D.G.; Baran, P.S. Innate C-H trifluoromethylation of heterocycles. Proc Natl Acad Sci USA 2011, 108 (35), 14411-5. PMID: 21844378.
Burés, J.; Armstrong, A.; Blackmond, D.G. Mechanistic rationalization of organocatalyzed conjugate addition of linear aldehydes to nitro-olefins. J Am Chem Soc 2011, 133 (23), 8822-5. PMID: 21568340.
Blackmond, D.G. The origin of biological homochirality. Philos Trans R Soc Lond B Biol Sci 2011, 366 (1580), 2878-84. PMID: 21930578.
Ferretti, A.C.; Brennan, C.; Blackmond, D.G. Reservoir catalysis: Rationalization of anomalous reaction orders in Pd-catalyzed amination of aryl halides. Inorg Chim Acta 2011, 369 (1), 292-295.
2010
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. J Am Chem Soc 2010, 132 (43), 15104-7. 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. J Am Chem Soc 2010, 132 (22), 7598-9. PMID: 20465280.
Blackmond, D.G. Kinetic aspects of non-linear effects in asymmetric synthesis, catalysis, and autocatalysis. Tetrahedron: Asymmetry 2010, 21 (11), 1630-1634.
Blackmond, D.G. The origin of biological homochirality. Cold Spring Harb Perspect Biol 2010, 2 (5), a002147. PMID: 20452962.
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. Angew Chem Int Ed Engl 2010, 49 (14), 2478-85. PMID: 20187051.
Viedma, C.; Verkuijl, B.J.; Ortiz, J.E.; de Torres, T.; Kellogg, R.M.; Blackmond, D.G. Solution-phase racemization in the presence of an enantiopure solid phase. Chemistry 2010, 16 (16), 4932-7. PMID: 20358554.