Highlights from the MacMillan Lab. Kelly Craft Group Meeting Presentation 7/8/15
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1 Highlights from the MacMillan Lab Kelly Craft Group Meeting Presentation 7/8/15
2 David MacMillan! Born in Bellshill, Scotland (1968)! Undergraduate degree: University of Gaslow (Ernie Colvin)! PhD: University of California, Irvine (Larry Overman)! Development of reaction methodology concerning stereocontrolled formation of bicyclic tetrahydrofurans! Total synthesis of 7-(-)-deacetoxyalcyonin acetate! Post doc: Harvard University (David Evans)! Design and development of Sn(II)-derived bisoxazoline complexes
3 David MacMillan! Independent research career! University of California, Berkeley ( )! California Institute of Technology ( )! Appointed Earle C. Anthony Professor of Chemistry in 2004! Princeton University (2006-current)! Appointed A. Barton Hepburn Professor of Chemistry in 2006
4 MacMillan Lab Major Areas of Research
5 Major Areas of Research I. Iminium catalysis II. Enamine catalysis III. SOMO catalysis IV. Photoredox catalysis
6 "New Strategies for Organic Catalysis: The First Highly Enantioselective Organocatalytic Diels-Alder Reaction"! Set in motion development of field of organocatalysis! Simultaneous publication from Carlos Barbas, Richard Lerner, and Benjamin List on enamine catalysis Ahrendt, K. A. et. al. J. Am. Chem. Soc. 2000, 122, List, B., Lerner, R. A. & Barbas, C. F. III. J. Am. Chem. Soc. 2000, 122, 2395.
7 First Highly Enantioselective Organocatalytic Diels-Alder Reaction: Initial Results Ahrendt, K. A. et. al. J. Am. Chem. Soc. 2000, 122, 4243.
8 First Highly Enantioselective Organocatalytic Diels-Alder Reaction: Reaction Scope Ahrendt, K. A. et. al. J. Am. Chem. Soc. 2000, 122, 4243.
9 Enantioselective Organocatalytic Intramolecular Diels-Alder Reaction Previously synthesized in 19 steps Shortened to just 9 steps Hagiwara, H. et. al. J. Org. Chem. 2002, 67, Wilson, R. M., et al. J. Am. Chem. Soc. 2005, 127,
10 Enantioselective Organocatalytic 1,3-Dipolar Cycloadditions! Lewis acid catalysis fails, but iminium catalysis does not O N Me Me Ph N H catalyst08 Me HClO 4 Jen W. S. et. al., J. Am. Chem. Soc. 2000, 122, 9874.
11 Enantioselective Organocatalytic Mukaiyama- Michael Reactions! Lewis acid catalysis fails, but iminium catalysis does not Brown, S. P. et. al. J. Am. Chem. Soc. 2003, 125, 1192.
12 Extensions of Iminium Catalysis Methodology! Friedel-Crafts pyrrole and indole alkylation! With development of indole alkylation methodology came development of new imidazolidinone catalyst Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, Austin, J.F. and MacMillan, D. W. C. J. Am. Chem. Soc. 2000, 124, 1172.
13 Extensions of Iminium Catalysis Methodology! Diels-Alder cycloaddition with simple α,β-unsaturated ketones Northrup, A. B. and MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 2458.! Hydride reduction Ouellet, S. G., et al. J. Am. Chem. Soc. 2005, 127, 32.
14 Extensions of Iminium Catalysis Methodology! Alkylation of aniline rings Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894.
15 Major Areas of Research I. Iminium catalysis II. Enamine catalysis III. SOMO catalysis IV. Photoredox catalysis
16 "The First Direct and Enantioselective Cross-Aldol Reaction of Aldehydes! Previous studies on catalytic enantioselective direct aldol reactions (e.g. intramolecular aldol, aldol between ketones and aldehydes)! No catalytic enantioselective method allowing for direct coupling of aldehyde substrates outside of enzymatic catalysis! Aldehydes tend to polymerize under metal-catalyzed conditions! Must have one aldehyde coupling partner consistently serve as nucleophilic donor and other as electrophilic donor Northrup, A. B. andmacmillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 6798.
17 Proline-Catalyzed Enamine Catalysis! Allowed for: I. Direct enantioselective aldehydealdehyde dimerization II. Direct enantioselective asymmetric cross-aldol Northrup, A. B. andmacmillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 6798.
18 Imidazolidinone-Catalyzed Cross-Aldol Reaction of Aldehydes! Secondary enamine additions generally progress via late stage transition state where formation of carbon-carbon bond is preceeded by development of iminium π bond (Houk and Bahmanyar, 2001) Bahmanyar, S. and Houk, K. N. J. Am. Chem. Soc., 2001, 123, Mangion, I. K., et al. Angew. Chem. Int. Ed. Engl. 2004, 43, 6722.
19 Imidazolidinone-Catalyzed Cross-Aldol Reaction of Aldehydes: Initial Results Mangion, I. K., et al. Angew. Chem. Int. Ed. Engl. 2004, 43, 6722.
20 Imidazolidinone-Catalyzed Cross-Aldol Reaction of Aldehydes: Reaction Scope Mangion, I. K., et al. Angew. Chem. Int. Ed. Engl. 2004, 43, 6722.
21 Use of Aldol Reactions for Two-Step Synthesis of Carbohydrates! Two required aldol reactions:! Enantioselective aldol between α-oxyaldehydes! Diastereoselective aldol between tri-oxy-substituted butanal and α-oxyaldehyde enolate Northrup, A. B. and MacMillan, D. W. C. Science 2004, 305, 1752.
22 Two-Step Synthesis of Carbohydrates: Initial Results Northrup, A. B. and MacMillan, D. W. C. Science 2004, 305, 1752.
23 Two-Step Synthesis of Carbohydrates: Reaction Scope Northrup, A. B. and MacMillan, D. W. C. Science 2004, 305, 1752.
24 Extensions of Enamine Catalysis Methodology! α-oxidation of aldehydes! α-chlorination of aldehydes Brown, S. P., et al. J. Am. Chem. Soc. 2003, 125, Brochu, M. P., et al. J. Am. Chem. Soc. 2004, 126, 4108.
25 Extensions of Enamine Catalysis Methodology! α-fluorination of aldehydes Beeson, T. D. and MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 8826.
26 Total Synthesis of Brasoside and Littoralisone: Use of Proline Catalysis in a Total Synthesis! First total synthesis of littoralisone: 13 steps in 13% overall yield Mangion, I. K. and MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 3696.
27 Total Synthesis of Brasoside and Littoralisone: Use of Proline Catalysis in a Total Synthesis Mangion, I. K. and MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 3696.
28 Total Synthesis of Brasoside and Littoralisone: Use of Proline Catalysis in a Total Synthesis Mangion, I. K. and MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 3696.
29 Total Synthesis of (+)-Minfiensine: Use of Cascade Organocatalysis Jones, S. B., Simmons, B. and MacMillan, D. W. C. J. Am. Chem. Soc. 2009, 131,
30 Total Synthesis of (+)-Minfiensine: Use of Cascade Organocatalysis Jones, S. B., Simmons, B. and MacMillan, D. W. C. J. Am. Chem. Soc. 2009, 131,
31 Total Synthesis of (+)-Minfiensine: Use of Cascade Organocatalysis! Previous syntheses: 15 steps in 6.5% overall yield (Overman); 12 steps in 4% overall yield (Qin)! This synthesis: 9 steps in 21% overall yield Shen, L. et. al. Agnew. Chem. Int. Ed. 2008, 47, Dounay, A. B. et. al. J. Am. Chem. Soc. 2008, 130, Jones, S. B., Simmons, B. and MacMillan, D. W. C. J. Am. Chem. Soc. 2009, 131,
32 Total Synthesis of (-)-Vincorine: Use of Cascade Organocatalysis! Previous syntheses: 31 steps in 1% overall yield (Qin); 18 steps in 5% overall yield (Ma)! This synthesis: 9 steps in 9% overall yield Zi, W.; Xie, W.; Ma, D. J. Am. Chem. Soc. 2012, 134, Zhang, M. et. al. J. Am. Chem. Soc. 2009, 131, Horning, B. D. and MacMillan D. W. C. J. Am. Chem. Soc. 2013, 135, 6442.
33 Total Synthesis of Diazonamide A: Use of Iminium Catalysis in a Total Synthesis! Previous syntheses: Nicolaou and Haran! This synthesis: 20 step longest linear sequence in 1.8% overall yield Nicolaou K.C. et. a;. J. Am. Chem. Soc., 2004, 126, Burgett, A. W. G. et. al. Angew. Chem., Int. Ed., 2003, 42, Knowles, R. R. et. al. Chem. Sci. 2011, 2, 308.
34 Total Synthesis of Diazonamide A: Use of Iminium Catalysis in a Total Synthesis Knowles, R. R. et. al. Chem. Sci. 2011, 2, 308.
35 Major Areas of Research I. Iminium catalysis II. Enamine catalysis III. SOMO catalysis IV. Photoredox catalysis
36 Enantioselective Organocatalysis Using SOMO Activation! Singly occupied molecular orbital activation! Mode of catalytic activation electronically intersecting iminium and enamine formation! Key points I. Enamine must be selectively oxidized in presence of amine catalyst, aldehyde substrate, and iminium ion precursor II. Amine catalyst must facilitate high levels of enantiocontrol in coupling of radical cation species with various π-rich nucleophiles Beeson, T. D., et al. Science, 2007, 316, 582.
37 SOMO Activation: Amine Catalyst! Density functional theory (DFT) calculations Beeson, T. D., et al. Science, 2007, 316, 582.
38 SOMO Activation: Reaction Scope and Mechanistic Studies Beeson, T. D., et al. Science, 2007, 316, 582.
39 SOMO Activation: Proposed Catalytic Cycle! Reaction cycle steps:! Condensation of 1 and 3! Enamine oxidation by Ce IV! Coupling of radical cation 6 and allyltrimethylsilane 2! Oxidation of 7 by Ce IV to intermediate 8! β-elimination of silyl cation through nucleophilic displacement! Hydrolysis of 9 to release product 4 and anime catalyst 3 Devery, J. J., 3rd, et al. Angew. Chem. Int. Ed. Engl. 2010, 49, 6106.
40 Extensions of SOMO Activation Methodology! α-enolation of aldehydes Jang, H-Y., Hong, J-B. and MacMillan, D. W. C. J. Am. Chem. Soc. 2007, 129, 7004.
41 Extensions of SOMO Activation Methodology! Carbo-oxidation of styrenes Graham, T. H. et. al. J. Am. Chem. Soc. 2008, 130,
42 Extensions of SOMO Activation Methodology! SOMO (4 + 2) cascade cycloaddition Jui, N. T., et al. J. Am. Chem. Soc. 2010, 132,
43 Extensions of SOMO Activation Methodology! SOMO (4 + 2) cascade cycloaddition Jui, N. T., et al. J. Am. Chem. Soc. 2010, 132,
44 Extensions of SOMO Activation Methodology! Intramolecular α-allylation of aldehydes using formal-tethered allylsilanes Pham, P. V., et al. Chem. Sci. 2011, 2, 1470.
45 Extensions of SOMO Activation Methodology! Intramolecular α-allylation of aldehydes using formal-tethered allylsilanes Pham, P. V., et al. Chem. Sci. 2011, 2, 1470.
46 Major Areas of Research I. Iminium catalysis II. Enamine catalysis III. SOMO catalysis IV. Photoredox catalysis
47 Merging of Photoredox and Organocatalysis: The Direct Asymmetric Alkylation of Aldehydes Nicewicz, D. A. and MacMillan, D. W. C. Science, 2008, 322, 77.
48 Merging of Photoredox and Organocatalysis: Proposed Photoredox Cycle! Organocatalytic cycle steps:! Condensation of amine catalyst 6 and aldehyde 7! Addition of SOMOphilic enamine 8 to electron-deficient radical 5! Oxidation of radical INT 9 to form iminium ion 10! Hydrolysis of 10 to release product and amine catalyst 6! Photoredox cycle steps:! Ru(bpy) 3 2+ photon acceptance to yield * Ru(bpy) 3 2+! * Ru(bpy) 3 2+ single electron oxidation of radical INT 9 to yield Ru(bpy) 3 + and iminium ion 10! Ru(bpy) 3 + single electron reduction of alkyl halide 4 to release electrondeficient radical 5 and Ru(bpy) 3 2+ Nicewicz, D. A. and MacMillan, D. W. C. Science, 2008, 322, 77.
49 Merging of Photoredox and Organocatalysis: Reaction Conditions! Amine catalyst must enforce high levels of enantiocontrol for coupling of π-rich enamine with electron-deficient radicals Nicewicz, D. A. and MacMillan, D. W. C. Science, 2008, 322, 77.
50 Merging of Photoredox and Organocatalysis: Reaction Scope and Control Studies! Control studies:! Exclusion of light! no presence of coupled product! Removal of Ru(bpy) 3 2+! <10% coupled product over extended timeframe (24 H)! Use of light source tuned to Ru(bpy) 3 2+ MLCT absorption band! dramatic acceleration in overall rate (90 min vs. 6 H) Nicewicz, D. A. and MacMillan, D. W. C. Science, 2008, 322, 77.
51 α-trifluromethylation of Aldehydes Nagib, D. A., et a. J. Am. Chem. Soc. 2009, 131,
52 α-trifluromethylation of Aldehydes: Reaction Scope Nagib, D. A., et a. J. Am. Chem. Soc. 2009, 131,
53 α-trifluromethylation of Carbonyl Compounds! Photoredox organocatalysis found to be extendable to ketones, esters, and amides! Via enolsilanes Pham, P. V., et al. Angew. Chem. Int. Ed. Engl. 2011, 50, 6119.
54 Trifluromethylation of Heteroaromatic Systems Nagib, D. A. and MacMillan, D. W. C,. Nature 2011, 480, 224.
55 Trifluromethylation of Heteroaromatic Systems: Reaction Scope Nagib, D. A. and MacMillan, D. W. C., Nature 2011, 480, 224.
56 β-arylation of Aldehydes and Ketones! Previous work showcased applicability of photoredox organocatalysis to α-benzylation of aldehydes! This work uses similar strategies for β-arylation of aldehydes and ketones Pirnot, M. T., et al. Science 2013, 339, Hui-Wen Shih, M. N. V. W., Grange R. L., and MacMillan, D. W. C. J. Am. Chem. Soc. 2010, 132,
57 β-arylation of Aldehydes and Ketones: Proposed Catalytic Cycle! Key step:! Key features of arene! Formation coupling of radical partner: cation 9 sufficiently! Radical formed weakens must be allylic electron C-H bond rich to enough allow to deprotenation discourage direct reaction with and subsequent enamine 8! formation Arenes as of electron β-enamine deficient as radical 1,4- dicyanobenzene 10 (5πe - can form long activation lived mode) radical anions (increases selectivity for radical coupling with β-enaminyl radical 10) Pirnot, M. T., et al. Science 2013, 339, 1593.
58 β-arylation of Aldehydes and Ketones: Reaction Scope Pirnot, M. T., et al. Science 2013, 339, 1593.
59 β-arylation of Aldehydes and Ketones: Reaction Scope
60 β-arylation of Aldehydes and Ketones: Reaction Scope Pirnot, M. T., et al. Science 2013, 339, 1593.
61 Arylation of Benzylic Ethers: Use of Thiol Organocatalyst! Looks to take advantage of weakness of allylic C-H bonds and weakly acidic nature of thiols Qvortrup, K. et. al. J. Am. Chem. Soc. 2014, 136, 626.
62 Arylation of Benzylic Ethers: Proposed Catalytic Cycle with Thiol Organocatalyst! Arylation of benzylic ethers! Thiol organocatalyst 6 undergoes proton-coupled electron transfer oxidation to generate thiyl radical 7 (first deprotonated to thiolate anion then oxidized to thiyl radical)! Thiyl radical 7 selectively abstracts H from substrate 8 where C-H bonds are weak and hydridic Qvortrup, K. et. al. J. Am. Chem. Soc. 2014, 136, 626.
63 Arylation of Allylic sp 3 C-H Bonds Cuthberson, J. D. and MacMillan D. W. C. Nature, 2015, 519, 74.
64 Arylation of Allylic sp 3 C-H Bonds: Proposed Catalytic Cycle Cuthberson, J. D. and MacMillan D. W. C. Nature, 2015, 519, 74.
65 Arylation of Allylic sp 3 C-H Bonds: Reaction Scope Cuthberson, J. D. and MacMillan D. W. C. Nature, 2015, 519, 74.
66 Extensions of Photoredox Organocatalysis Methodology! Amine α-heteroarylation Prier, C. K. and MacMillan, D. W. C. Chem. Sci. 2014, 5, 4173.! Decarboxylative arylation of α-amino acids Zuo, Z. and MacMillan, D. W. C. J. Am. Chem. Soc. 2014, 136, 5257.
67 Extensions of Photoredox Organocatalysis Methodology! β-alkylation of aldehydes Terrett, J. A., et al. J. Am. Chem. Soc. 2014, 136, 6858.
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