Oxy-Allyl Cation Catalysis: An Enantioselective Electrophilic Activation Mode

Chun Liu; E. Zachary Oblak; Mark N. Vander Wal; Andrew K. Dilger; Danielle K. Almstead; David W.C. MacMillan

doi:10.1021/jacs.5b13041

Oxy-Allyl Cation Catalysis: An Enantioselective Electrophilic Activation Mode

Chun Liu, E. Zachary Oblak, Mark N. Vander Wal, Andrew K. Dilger, Danielle K. Almstead, David W.C. MacMillan

Chemistry

Research output: Contribution to journal › Article › peer-review

51 Scopus citations

Abstract

A generic activation mode for asymmetric LUMO-lowering catalysis has been developed using the long-established principles of oxy-allyl cation chemistry. Here, the enantioselective conversion of racemic α-tosyloxy ketones to optically enriched α-indolic carbonyls has been accomplished using a new amino alcohol catalyst in the presence of electron-rich indole nucleophiles. Kinetic studies reveal that the rate-determining step in this S_N1 pathway is the catalyst-mediated α-tosyloxy ketone deprotonation step to form an enantiodiscriminant oxy-allyl cation prior to the stereodefining nucleophilic addition event.

Original language	English (US)
Pages (from-to)	2134-2137
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	7
DOIs	https://doi.org/10.1021/jacs.5b13041
State	Published - Mar 2 2016

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.5b13041

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title = "Oxy-Allyl Cation Catalysis: An Enantioselective Electrophilic Activation Mode",

abstract = "A generic activation mode for asymmetric LUMO-lowering catalysis has been developed using the long-established principles of oxy-allyl cation chemistry. Here, the enantioselective conversion of racemic α-tosyloxy ketones to optically enriched α-indolic carbonyls has been accomplished using a new amino alcohol catalyst in the presence of electron-rich indole nucleophiles. Kinetic studies reveal that the rate-determining step in this SN1 pathway is the catalyst-mediated α-tosyloxy ketone deprotonation step to form an enantiodiscriminant oxy-allyl cation prior to the stereodefining nucleophilic addition event.",

author = "Chun Liu and Oblak, {E. Zachary} and {Vander Wal}, {Mark N.} and Dilger, {Andrew K.} and Almstead, {Danielle K.} and MacMillan, {David W.C.}",

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doi = "10.1021/jacs.5b13041",

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T1 - Oxy-Allyl Cation Catalysis

T2 - An Enantioselective Electrophilic Activation Mode

AU - Liu, Chun

AU - Oblak, E. Zachary

AU - Vander Wal, Mark N.

AU - Dilger, Andrew K.

AU - Almstead, Danielle K.

AU - MacMillan, David W.C.

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AB - A generic activation mode for asymmetric LUMO-lowering catalysis has been developed using the long-established principles of oxy-allyl cation chemistry. Here, the enantioselective conversion of racemic α-tosyloxy ketones to optically enriched α-indolic carbonyls has been accomplished using a new amino alcohol catalyst in the presence of electron-rich indole nucleophiles. Kinetic studies reveal that the rate-determining step in this SN1 pathway is the catalyst-mediated α-tosyloxy ketone deprotonation step to form an enantiodiscriminant oxy-allyl cation prior to the stereodefining nucleophilic addition event.

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Oxy-Allyl Cation Catalysis: An Enantioselective Electrophilic Activation Mode

Abstract

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