David W.C. MacMillan: Career-in-Review. Yan Xu Dong Group Meeting Jan. 2, 2014
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1 David W.C. MacMillan: Career-in-Review Yan Xu Dong Group Meeting Jan. 2, 2014
2 David W.C. MacMillan: A Brief Introduction Career 1968 Born in Bellshill, Scotland Undergraduate degree in chemistry at the University of Glasgow Doctoral studies with Professor Larry E. Overman at the University of California, Irvine Postdoctoral studies with Professor David Evans at the Harvard University. July 1998 Dave began his independent research career at the University of California, Berkeley. June 2000 Joined the department of chemistry at CIT June 2006 Appointed as the A. Barton Hepburn Professor of Chemistry at Princeton University. Title James S. McDonnell Distinguished University Professor of Chemistry at Princeton University. Chairperson of the Department of Chemistry at Princeton University. Director of the Merck Center for Catalysis at Princeton University Present Chemical Science [Editor-in-Chief]
3 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
4 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
5 The First Highly Enantioselective Organocatalytic Diels-Alder Reactions two way to lower the LUMO of the enal system designed reaction cycle J. Am. Chem. Soc. 2000, 122,
6 The First Highly Enantioselective Organocatalytic Diels-Alder Reactions origin of chiral control 12 examples, 85-96% ee, 72-99% yield E isomer J. Am. Chem. Soc. 2000, 122,
7 The First Highly Enantioselective Organocatalytic Diels-Alder Reactions origin of chiral control 12 examples, 85-96% ee, 72-99% yield Shield the Re face E isomer J. Am. Chem. Soc. 2000, 122,
8 The First Highly Enantioselective Organocatalytic Diels-Alder Reactions synthesis of Solanapyrone J. Am. Chem. Soc., 2005, 127,
9 Highly enantioselective [3+2] cycloaddition reaction nitrone as the sustrate screening of catalyst J. Am. Chem. Soc. 2000, 122,
10 Highly enantioselective [3+2] cycloaddition reaction nitrone as the sustrate screening of catalyst J. Am. Chem. Soc. 2000, 122,
11 Highly enantioselective [3+2] cycloaddition reaction nitrone as the sustrate screening of catalyst J. Am. Chem. Soc. 2000, 122,
12 Highly enantioselective [3+2] cycloaddition reaction nitrone as the sustrate screening of the acid cocatalyst J. Am. Chem. Soc. 2000, 122,
13 The First Enantioselective Organocatalytic Friedel-Crafts Alkylation very sensitive to the cocatalyst J. Am. Chem. Soc. 2001, 123,
14 The First Enantioselective Organocatalytic Friedel-Crafts Alkylation 1,2-addtion is highly prohibited by the catalyst calculated iminium ion model J. Am. Chem. Soc. 2001, 123,
15 Enantioselective Indole Alkylation previous reaction initial trial High yield Good ee value J. Am. Chem. Soc. 2001, 123, Sluggish reaction Poor ee value J. Am. Chem. Soc., 2002, 124,
16 Enantioselective Indole Alkylation previous reaction initial trial High yield Good ee value J. Am. Chem. Soc. 2001, 123, Sluggish reaction Poor ee value J. Am. Chem. Soc., 2002, 124,
17 faster iminium formation increased Si-face coverage J. Am. Chem. Soc., 2002, 124,
18 faster iminium formation increased Si-face coverage & unhindered Re-face J. Am. Chem. Soc., 2002, 124,
19 Enantioselective Indole Alkylation with new catalyst J. Am. Chem. Soc., 2002, 124,
20 Other Enantioselective Friedel-Crafts Type Alkylations aniline as nucleophile 25 examples, 66-97% yield, % ee J. Am. Chem. Soc., 2002, 124, silyloxy furan as nucleophile DBNA = 2,4-dinitrobenzoic acid (DBNA) 12 examples, 80-93% yield, % ee J. Am. Chem. Soc., 125, (2003
21 Other Enantioselective Friedel-Crafts Type Alkylations aniline as nucleophile 25 examples, 66-97% yield, % ee J. Am. Chem. Soc., 2002, 124, silyloxy furan as nucleophile DBNA = 2,4-dinitrobenzoic acid (DBNA) 12 examples, 80-93% yield, % ee J. Am. Chem. Soc., 2003, 125,
22 Other Enantioselective Friedel-Crafts Type Alkylations Trifluoroborate salts (Molander reagent) as nucleophile 91 % yield, 95 % ee 85 % yield, 95 % ee J. Am. Chem. Soc., 2007, 129,
23 The First General Enantioselective Catalytic Diels-Alder Reaction with Simple α,β-unsaturated Ketones regular chiral metal catalyst is difficult to distinguish the two asymmetric lone pair catalyst screening % yield, % ee J. Am. Chem. Soc., 2002, 124,
24 Organic Catalyzed Reduction in Biological Systems J. Am. Chem. Soc., 2005, 127, 32-33
25 Enantioselective Organocatalytic Hydride Reduction Hantzsch ester: analogue of NADH LUMO lowing amine catalyst: analogue of enzyme catalyst screening J. Am. Chem. Soc., 127, (2005)
26 Enantioselective Organocatalytic Hydride Reduction Hantzsch ester: analogue of NADH LUMO lowing amine catalyst: analogue of enzyme catalyst screening J. Am. Chem. Soc., 2005, 127, 32-33
27 Enantioselective Organocatalytic Hydride Reduction Hantzsch ester: analogue of NADH LUMO lowing amine catalyst: analogue of enzyme substrate scope research: strong chiral control ability 95 % yield, 91 % ee J. Am. Chem. Soc., 2005, 127, 32-33
28 Enantioselective Organocatalytic Hydride Reduction Hantzsch ester: analogue of NADH LUMO lowing amine catalyst: analogue of enzyme In 2006, further expanded to cyclic enone substrate! 12 examples (5-7 member rings) % yield, % ee J. Am. Chem. Soc., 2006, 128,
29 Enantioselective Cyclopropanation Reaction Catalyst screening: only L-proline gives the desired product! Why? poor Z/E control electrostatic directing effect J. Am. Chem. Soc., 2005, 127,
30 Enantioselective Cyclopropanation Reaction Catalyst screening: only L-proline gives the desired product! Why? poor Z/E control electrostatic directing effect J. Am. Chem. Soc., 2005, 127,
31 Enantioselective Cyclopropanation Reaction Catalyst screening: only L-proline gives the desired product! Why? single Z isomer electrostatic directing effect J. Am. Chem. Soc., 2005, 127,
32 Enantioselective Cyclopropanation Reaction Catalyst screening: only L-proline gives the desired product! Why? single Z isomer electrostatic directing effect J. Am. Chem. Soc., 2005, 127,
33 Enantioselective Amination Reaction Iminum catalyzed amination requires selective amine partition Carbamate is good, but with poor nucleophilicity Carbamate nucleophilicity enhanced by α-effect 92 % yield, 92 % ee J. Am. Chem. Soc., 2006, 128,
34 Enantioselective Amination Reaction Iminum catalyzed amination requires selective amine partition Carbamate is good, but poor nucleophilicity Carbamate nucleophilicity enhanced by α-effect 92 % yield, 92 % ee J. Am. Chem. Soc., 2006, 128,
35 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
36 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
37 Enantioselective Aldol Reaction Aldehyde dimerization 91 % yield, 3:1 dr, 99 % ee Aldehyde cross-aldol reaction: with non-enaminizable aldehyde syringe pump addition 87 % yield, 14:1 dr, 99 % ee 81 % yield, 3:1 dr, 99 % ee 80 % yield, 24:1 dr, 98 % ee J. Am. Chem. Soc., 2002, 124,
38 Enantioselective Aldol Reaction Aldehyde dimerization 91 % yield, 3:1 dr, 99 % ee Aldehyde cross-aldol reaction: with non-enaminizable aldehyde syringe pump addition 87 % yield, 14:1 dr, 99 % ee 81 % yield, 3:1 dr, 99 % ee 80 % yield, 24:1 dr, 98 % ee J. Am. Chem. Soc., 2002, 124,
39 Enantioselective Aldol Reaction:Further Expansion α-oxy-aldehyde dimerization 73 % yield, 4:1 dr, 98 % ee Cross-aldol reaction: with non-enaminizable aldehyde 75 % yield, 4:1 dr, 99 % ee Here as Aldol acceptor Differs with metal mediated reaction Angew. Chem. Int. Ed. 2004, 43, Angew. Chem. Int. Ed. 2004, 43,
40 Enantioselective Aldol Reaction:Further Expansion 2 monosaccharide synthesis! Science, 2004, 305,
41 Enantioselective Aldol Reaction:Further Expansion 2 monosaccharide synthesis! Science, 2004, 305,
42 Enantioselective Aldol Reaction:Further Expansion 2 monosaccharide synthesis! Science, 2004, 305,
43 HOMO Catalysis: other than Aldol α-oxidation of Aldehydes 8 examples, % yield, % ee α-chlorination of Aldehydes J. Am. Chem. Soc., 2003, 125, examples, % yield, % ee J. Am. Chem. Soc., 2004, 126,
44 HOMO Catalysis: other than Aldol α-oxidation of Aldehydes 8 examples, % yield, % ee α-chlorination of Aldehydes J. Am. Chem. Soc., 2003, 125, the Leckta quinone 7 examples, % yield, % ee J. Am. Chem. Soc., 2004, 126,
45 HOMO Catalysis: other than Aldol α-fluorination of Aldehydes α-trifluoromethylation of Aldehydes 54-96% yield, 91-99% ee For the α-fluorination of cyclic ketone using cinchonine-type catalyst, see: J. Am. Chem. Soc., 2011, 133, J. Am. Chem. Soc., 2005, 127, Togni reagent 70-87% yield, 93-97% ee J. Am. Chem. Soc., 2010, 132,
46 HOMO Catalysis: other than Aldol α-fluorination of Aldehydes α-trifluoromethylation of Aldehydes 54-96% yield, 91-99% ee For the α-fluorination of cyclic ketone using cinchonine-type catalyst, see: J. Am. Chem. Soc., 2011, 133, J. Am. Chem. Soc., 2005, 127, Togni reagent 70-87% yield, 93-97% ee J. Am. Chem. Soc., 2010, 132,
47 HOMO Catalysis: other than Aldol α-oxidation of Aldehydes 49-80% yield, % ee
48 HOMO Catalysis: other than Aldol α-oxidation of Aldehydes 49-80% yield, % ee Baerends, E. J. Inorg. Chem. 2009, 48, J. Am. Chem. Soc., 2010, 132,
49 HOMO Catalysis: other than Aldol α-arylation of Aldehydes diphenyl iodonium 22 examples, 90-94% ee J. Am. Chem. Soc., 2011, 133,
50 diphenyl iodonium 22 examples, 90-94% ee proposed mechanism For studies on the mechanism of copper-catalyzed arylation, see: (a) Lockhart, T. P. J. Am. Chem. Soc. 1983, 105, (b) Beringer, F. M.; Geering, E. J.; Kuntz, I.; Mausner, M. J. Phys. Chem. 1956, 60, 141. J. Am. Chem. Soc., 2011, 133, 4260
51 diphenyl iodonium 22 examples, 90-94% ee Further expansion to ester and amide substrate: the use of enolsilane enolsilane X = OR, NR 2 chiral Cu(I) salt no chiral amine catalyst 94% yield, 93% ee 79% yield, 90% ee J. Am. Chem. Soc., 2011, 133,
52 Not belong to the HOMO catalysis, but stongly related: using indole as the nucleophile instead of enolsilane chiral Cu(I) salt Similar mechanism: J. Am. Chem. Soc., 2012, 134,
53 HOMO catalysis: Further development α-arylation of Aldehydes diphenyl iodonium 22 examples, 90-94% ee α-vinylation α-vinylation of Aldehydes of Aldehydes Identical catalyst combination 18 examples, 91-99% ee Substrate scope & CuBr Vinyl hypervalent iodide J. Am. Chem. Soc., 2012, 134,
54 HOMO catalysis: Further development Combination of vinyl boronic acid and O 2 80% yield, 95% ee 73% yield, 90% ee J. Am. Chem. Soc., 2013, 135,
55 Not belong to the HOMO catalysis, but stongly related: Same strategy: Cu salt + organic feedstock + O 2 Proposed Mechanism: Substrate scope 91% yield 67% yield 90% yield J. Am. Chem. Soc., 2013, 135,
56 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
57 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
58 Cascade Catalysis: Merging HOMO and LUMO Activation Imidazolldinones: Organocatalysts for HOMO or LUMO Activation Cascade Catalysis: Merging HOMO and LUMO Activation with one catalyst J. Am. Chem. Soc., 2005, 127,
59 Cascade Catalysis: Merging HOMO and LUMO Activation J. Am. Chem. Soc., 2005, 127,
60 Cascade Catalysis: Enantioselective β-aryl-α-chlorination Substrate scope 86% yield, 99% ee, 14:1 dr J. Am. Chem. Soc., 2005, 127,
61 Cascade Catalysis: Enantioselective β-aryl-α-chlorination 86% yield, 99% ee, 14:1 dr Substrate scope Large Bn-indole side chain: Higher shield of the upward side overcome the substrate control in the second catalytic circle J. Am. Chem. Soc., 2005, 127,
62 Cascade Catalysis: Enantioselective β-aryl-α-chlorination Substrate scope 86% yield, 99% ee, 14:1 dr J. Am. Chem. Soc., 2005, 127,
63 Cascade Catalysis: More reaction types Modular combination of proline and Macmillan amine Macmillan amine: Iminium catalyst Proline: Enamine catalyst Angew. Chem. Int. Ed., 2009, 48,
64 Cascade Catalysis: More reaction types Modular combination of proline and Macmillan amine Combination A : R, R Combination B : R, S Angew. Chem. Int. Ed., 2009, 48,
65 Combination A : R, R Combination B : R, S Enantioselective Hydro-Amination: Enantioselective Hydro-Oxidation: Angew. Chem. Int. Ed., 2009, 48, 4349
66 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
67 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
68 HOMO catalyst: inefficient with some nucleophile Potential issues for enantioselective alkylation using HOMO catalysis insufficient e- density to react with sp3- ekectrophile sufficient e- density to react with sp2- ekectrophile
69 New Idea: SOMO catalysis after a SET process SET oxidant HOMOphile (allyl bromide) SOMOphile (allyl silane) SOMO intermediate: same chiral control as HOMO intermediate Science, 2007, 316,
70 New Idea: SOMO catalysis after a SET process HOMOphile (allyl bromide) SOMOphile (allyl silane) SOMO intermediate: same chiral control as HOMO intermediate Science, 2007, 316,
71 New Idea: SOMO catalysis after a SET process HOMOphile (allyl bromide) SOMOphile (allyl silane) SOMO intermediate: same chiral control as HOMO intermediate Science, 2007, 316,
72 Science, 2007, 316, New Idea: SOMO catalysis after a SET process HOMOphile (allyl bromide) SOMOphile (allyl silane) SOMO intermediate: same chiral control as HOMO intermediate
73 SOMO catalysis: Enantioselective Aldehyde α-allylation CAN: selective oxidant Reaction condition: Substrate scope: Science, 2007, 316,
74 SOMO catalysis: Enantioselective Aldehyde α-allylation CAN: selective oxidant Reaction condition: Substrate scope: Science, 2007, 316,
75 SOMO catalysis: the proof of the machenism
76 SOMO catalysis: the proof of the machenism Radical-Cation Intermediate? Radical Clock Experiment 1: Radical Clock Experiment 2:
77 SOMO catalysis: the proof of the machenism Radical-Cation Intermediate? Radical Clock Experiment 1: Radical Clock Experiment 2:
78 SOMO catalysis: the proof of the machenism Radical or Carbocation? radical clock & cation clock
79 SOMO catalysis: the proof of the machenism Radical or Carbocation? Experiment result: radical-pathway product
80 SOMO catalysis: the proof of the machenism Radical or Carbocation? Experiment result: radical-pathway product
81 SOMO catalysis: the proof of the machenism Second SET oxidation?
82 SOMO catalysis: the proof of the machenism SOMOphile: electron rich nucleophile with the ability to stablized a new generated radical For the intramolecular version, see: Chem. Sci., 2011, 2, For the SOMO allylation of cyclic ketone, see: Proc. Nat. Acad. Sci. USA, 2010, 107,
83 SOMO catalysis: More than allylation Aldehyde α-enolation 85% yield, 90% ee Aldehyde α-vinylation J. Am. Chem. Soc., 2007, 129, % yield, 94% ee Styrene carbo-oxidation J. Am. Chem. Soc., 2008, 130, % yield, 96% ee J. Am. Chem. Soc., 2008, 130, For the styrene carbo-amination, see: J. Am. Chem. Soc., 2012, 134,
84 SOMO catalysis: More than allylation Epoxidation 85% yield, 95% ee Angew. Chem. Int. Ed., 2009, 48, α-arylation 86% yield, 95% ee α-nitroalkylation J. Am. Chem. Soc., 2009, 131, % yield, 87% ee, dr = 6:1 J. Am. Chem. Soc., 2009, 131,
85 SOMO catalysis: More than allylation Polyene cyclization 11 contiguous stereocenters 62% yield Enantioenriched polycyclo Propagating species is radical: alternating polarity favors cyclization J. Am. Chem. Soc., 2010, 132, For an extremely similar intramolecular homo-ene reaction of aldehyde, see: J. Am. Chem. Soc., 2013, 135,
86 SOMO catalysis: Nature of Intermediates in Organo-SOMO Catalysis Calculation study SOMO orbital is mainly on the β-carbon can be best characterized as an alkyl radical conjugated to an iminium cation consistent with the previous mechanism hypothesis J. Am. Chem. Soc., 2010, 132,
87 SOMO catalysis: Nature of Intermediates in Organo-SOMO Catalysis Calculation study SOMO orbital is mainly on the β-carbon can be best characterized as an alkyl radical conjugated to an iminium cation consistent with the previous mechanism hypothesis J. Am. Chem. Soc., 2010, 132,
88 SOMO catalysis: Nature of Intermediates in Organo-SOMO Catalysis Calculation study SOMO orbital is mainly on the β-carbon can be best characterized as an alkyl radical conjugated to an iminium cation consistent with the previous mechanism hypothesis J. Am. Chem. Soc., 2010, 132,
89 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
90 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
91 New Catalysis:Merge the Organo Catalyst and the Photo Redox Catalyst Enantioselective Catalytic Carbonyl α-alkylation: A brief design + hv Enamine (SOMOphile) + Alkyl radical Science, 2008, 322, 77-80
92 New Catalysis:Merge the Organo Catalyst and the Photo Redox Catalyst Ru(bpy) 3 2+ * excited ligand-based state Science, 2008, 322, 77-80
93 New Catalysis:Merge the Organo Catalyst and the Photo Redox Catalyst Enantioselective Catalytic Carbonyl α-alkylation Catalyst Combination Substrate scope 93% yield, 90% ee 84% yield, 96% ee 80% yield, 92% ee Science, 2008, 322, 77-80
94 Enantioselective Photo-redox Organo Catalysis Enantioselective α-trifluoromethylation 79% yield, 99% ee 61% yield, 93% ee 89% yield, 99% ee J. Am. Chem. Soc., 2009, 131,
95 Enantioselective Photo-redox Organo Catalysis Enantioselective α-trifluoromethylation J. Am. Chem. Soc., 2009, 131, Enantioselective α-benzylation fac-ir(ppy) 3 Reductive potential for excited state: E 1/2 = -1.73V substrate: only electron deficient aromatic compound J. Am. Chem. Soc., 2010, 132,
96 Enantioselective Photo-redox Organo Catalysis Enantioselective α-trifluoromethylation J. Am. Chem. Soc., 2009, 131, Racemic α-trifluoromethylation: Start from enolsilane amide ester ketone 76 % 85 % 72 % Angew. Chem. Int. Ed., 2011, 50,
97 Enantioselective Photo-redox Organo Catalysis Enantioselective α-amination ODNs = 2,4-dinitrophenylsulfonyloxy, a photolabile LG CO 2 R 1 = CO 2 Me, CBz, Boc Mechanism: 18 examples, 86-94% ee For the direct Coupling of α-carbonyls with Functionalized Amines, see: J. Am. Chem. Soc., 2013, 135, J. Am. Chem. Soc., 2013, 135,
98 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
99 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
100 Photo-redox Catalysis: a different type & via high throughput screening Science, 2011, 334,
101 Photo-redox Catalysis: a different type & via high throughput screening E 1/2, red = 1.61 V E 1/2, ox = 1.73 V Science, 2011, 334,
102 Photo-redox Catalysis: for β-functionalization Science, 2013, 339,
103 Photo-redox Catalysis: for β-functionalization deprotonation prefer the allyl position rather than the α-position Science, 2013, 339,
104 Photo-redox Catalysis: for β-functionalization Substrate scope 79 % 78 % 70 % 88 % For cyclic ketone Science, 2013, 339,
105 Photo-redox Catalysis: β-functionalization For benzophenone substrate For arylalkylketone substrate J. Am. Chem. Soc. 2013, 135,
106 Photo-redox Catalysis: β-functionalization For benzophenone substrate For arylalkylketone substrate J. Am. Chem. Soc. 2013, 135,
107 Photo-redox Catalysis: β-functionalization For benzophenone substrate Substrate scope For arylalkylketone substrate 81 % 70 % J. Am. Chem. Soc. 2013, 135, % 79 %
108 Photo-redox Catalysis: Arene Trifluoromethylation Photocatalyst = Ru(phen) 3 Cl 2 CF3 radical comes from CF 3 SO 2 Cl Nature, 2011, 480,
109 Photo-redox Catalysis: Arene Trifluoromethylation Proposed mechanism: Ru(phen)3Cl2 Nature, 2011, 480,
110 Photo-redox Catalysis: Arene Trifluoromethylation Substrate scope: hetereo arene & electron-rich arene
111 Photo-redox Catalysis: Arene Trifluoromethylation Substrate scope: hetereo arene & electron-rich arene
112 Photo-redox Catalysis: Arene Trifluoromethylation Substrate scope: hetereo arene & electron-rich arene conjugated (more stable) cross-conjugated (less stable)
113 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
114 Content 1 LUMO Catalysis 2 HOMO Catalysis 3 Cascade LUMO-HOMO Catalysis 4 SOMO Catalysis 5 Photoredox Organo Catalysis 6 Photoredox Organo Catalysis (Type II) 7 Summary
115 Summary
116 Summary
117 Summary New chiral amine catalyst family Merge different type of catalysis Deep-going mechanism study
118 Summary New chiral amine catalyst family Merge different type of catalysis Deep-going mechanism study
119
120 Q1 75 % yield, 4:1 dr, 99 % ee Here as Aldol acceptor Differs with metal mediated reaction J. Am. Chem. Soc., 2002, 124,
121 Q2 α-oxidation of Aldehydes 49-80% yield, % ee Baerends, E. J. Inorg. Chem. 2009, 48, J. Am. Chem. Soc., 2010, 132,
122 Q3 E 1/2, red = 1.61 V E 1/2, ox = 1.73 V Science, 2011, 334,
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