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Asymmetric Counteranion-Directed
Catalysis
M1 Yuki Hirao
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2
Contents
1. Introduction・ACDC
・BINOL-derived chiral catalyst
2. Applications・Mukaiyama aldol reaction
・Diels-Alder reaction
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3
Contents
1. Introduction・ACDC
・BINOL-derived chiral catalyst
2. Applications・Mukaiyama aldol reaction
・Diels-Alder reaction
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Benjamin List
https://www.kofo.mpg.de/en/research/homogeneous-catalysis-
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What is ACDC?
M. Mahlau, B. List, Angew. Chem. Int. Ed. 2013, 52, 518.
ACDC : Asymmetric Counteranion-Directed Catalysis
Asymmetric counteranion-directed catalysis refers to the
induction of enantioselectivity in a reaction proceeding
through a cationic intermediate by means of ion pairing
with a chiral, enantiomerically pure anion provided by the
catalyst.
Phase-Transfer Catalysis ACDC
P=product
S=substrate
X=anion
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Example of ACDC
S.Mayer, B. List, Angew. Chem. Int. Ed. 2006, 45, 4193.
G. L. Hamilton, E. J. Kang, M. Mba, F. D. Toste, Science. 2007, 317, 496.
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Silylium Lewis Acid Catalysis
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“Silylium” ACDC
DOI: 10.1002/anie.201900932
P=product
Nu=nucleophile
E=electrophile
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9
Contents
1. Introduction・ACDC
・BINOL-derived chiral catalyst
2. Applications・Mukaiyama aldol reaction
・Diels-Alder reaction
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BINOL-Derived Chiral Catalyst
D. Uraguchi, M, Terada, J. Am. Chem. Soc. 2004, 126, 5356.
T. Akiyama, J. Itoh, K. Yokota, K, Fuchibe, Angew. Chem. Int. Ed. 2004, 43, 1566.
first report of BINOL-derived phosphoric acid
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BINOL-Derived Chiral Catalyst
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Imidodiphosphorimidate (IDPi)
DOI: 10.1002/anie.201900932
reactivity
selectivity
Imidodiphosphorimidate (IDPi)
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IDPi Catalyst
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Applications
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15
Contents
1. Introduction・ACDC
・BINOL-derived chiral catalyst
2. Applications・Mukaiyama aldol reaction
・Diels-Alder reaction
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Mukaiyama Aldol Reaction
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Single Aldolization
L. Schreyer, P. S. J. Kaib, V. N. Wakchaure, C. Obradors, R. Properzi, S. Lee, B. List, Science. 2018, 362, 216.
M. B. Boxer, H. Yamamoto, J. Am. Chem, Soc. 2006, 128, 48.
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Previously Reported Catalyst
P. Garcia, F. Lay, P. Garcia, C. Rabalakos, B. List, Angew. Chem. Int. Ed. 2009, 48, 4363.
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Previously Reported Catalyst
P. Garcia, F. Lay, P. Garcia, C. Rabalakos, B. List, Angew. Chem. Int. Ed. 2009, 48, 4363.
○ aromatic aldehyde
○ catalyst loading
△ ketene silyl acetal
× aliphatic aldehyde
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Catalyst Optimization (Aromatic Aldehyde)
L. Schreyer, P. S. J. Kaib, V. N. Wakchaure, C. Obradors, R. Properzi, S. Lee, B. List, Science. 2018, 362, 216.
・meta and para-substituted phenyl
group(R1) of the IDPi revealed a
profound enhancement of
enantioselectivity.
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21L. Schreyer, P. S. J. Kaib, V. N. Wakchaure, C. Obradors, R. Properzi, S. Lee, B. List, Science. 2018, 362, 216.
Catalyst Optimization (Aliphatic Aldehyde)
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Substrate Scope
L. Schreyer, P. S. J. Kaib, V. N. Wakchaure, C. Obradors, R. Properzi, S. Lee, B. List, Science. 2018, 362, 216.
Reactions were performed with 0.5 mmol of aldehydes. *Using IDPi 4c. †Using IDPi 4d and 1.4 equivalents of enolsilane 2b. ‡Using IDPi 4d and
1.2 equivalents of enolsilane 2b.§Using IDPi 4e. ||Reactions were performed in CHCl3/n-hexane (5:4) at −78℃ using IDPi 4e.
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Catalyst and Silyl Group
L. Schreyer, P. S. J. Kaib, V. N. Wakchaure, C. Obradors, R. Properzi, S. Lee, B. List, Science. 2018, 362, 216.
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Proposed Catalytic Cycle
L. Schreyer, P. S. J. Kaib, V. N. Wakchaure, C. Obradors, R. Properzi, S. Lee, B. List, Science. 2018, 362, 216.
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Enantioselectivity
L. D. Amico, F. Zanardi, Angew. Chem. Int. Ed. 2019, 58, 3264L. Schreyer, P. S. J. Kaib, V. N. Wakchaure, C. Obradors, R. Properzi, S. Lee, B. List, Science. 2018, 362, 216.
IDPiIDPi
IDPipproduct
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Single Reaction
DOI: 10.1002/anie.201900932
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Mukaiyama Aldol Reaction
L. D. Amico, F. Zanardi, Angew. Chem. Int. Ed. 2019, 58, 3264.
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28
Contents
1. Introduction・ACDC
・BINOL-derived chiral catalyst
2. Applications・Mukaiyama aldol reaction
・Diels-Alder reaction
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Diels-Alder Reaction (ACDC)
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
T. Gatzenmeier, M. Gemmeren, Y. Xie, D. Höfler, M. Leutzsch, B. List, Science, 2016, 351, 949.
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Initial Try
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
DSI
cat 1
BALT
cat 2 IDPi
cat 3 cat 4 cat 5
cat 6 cat 7
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Reaction Development
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
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Substrate Scope
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
awith catalyst 4a; bwith catalyst 4b;cwith catalyst 4c; dwith catalyst 4d (3 mol %).
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33
Substrate Scope
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
awith catalyst 4a; bwith catalyst 4b;cwith catalyst 4c; dwith catalyst 4d (3 mol%).
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Catalyst Recycling
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
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Scale-up Experiments
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
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Proposed Catalytic Cycle
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
T. Gatzenmeier, M. Gemmeren, Y. Xie, D. Höfler, M. Leutzsch, B. List, Science. 2016, 351, 949.
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37
Computational Studies
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
catalyst activation
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Most Favorable Transition State
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
N
O
F
S
P
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Interaction with the Chiral Ion Pair
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
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Summary・ Asymmetric Counteranion-Directed Catalysis
(ACDC) concept is well developed.
・BINOL-derived new IDPi catalyst promotes
various kinds of reactions.
➢ extremely low catalyst loading
→high turnover, hydrolytically stable
➢ highly selective catalysis
→highly confined enantiopure catalysis
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Appendix
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Synthesis of Catalysts
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
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43
Mechanistic Study (MAR)
P. Garcia, F. Lay, P. Garcia, C. Rabalakos, B. List, Angew. Chem. Int. Ed. 2009, 48, 4363.
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44
Scaled-up Aldol Reaction
L. Schreyer, P. S. J. Kaib, V. N. Wakchaure, C. Obradors, R. Properzi, S. Lee, B. List, Science. 2018, 362, 216.
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45
Graphical Method of Burés
L. Schreyer, P. S. J. Kaib, V. N. Wakchaure, C. Obradors, R. Properzi, S. Lee, B. List, Science. 2018, 362, 216.
single IDPi molecule is responsible for the activation of aldehyde
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Self Repair Cycle
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47
Computational Studies
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671.
catalyst activation
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pKa of Catalyst
H. Y. Bae, D. Höfler, P. S. J. Kaib, P. Kasaplar, C. K. De, A. Döhring, S. Lee, K. Kaupmees, I. Leito, B. List, Nat. Chem. 2018, 10, 888
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Electrophilic Reactivities of Michael Acceptors
D. S. Allgauer, H. Jangra, H. Asahara, Z. Li, Q. Chen, H. Zipse, A. R. Ofial, H. Mayr, J. Am. Chem. Soc. 2017, 139, 13318.
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Catalyst Methylation
T. Gatzenmeier, M. Turberg, D. Yepes, Y. Xie, F. Neese, G. Bistoni, B. List, J. Am. Chem. Soc. 2018, 140, 12671