DFT Study of the Strong Solvent Effects in the Cu-Catalyzed Asymmetric Conjugate Addition Reaction

Zheng Ling; Fang Xie; Ilya D. Gridnev; Wanbin Zhang

doi:10.1002/jccs.201700263

DFT Study of the Strong Solvent Effects in the Cu-Catalyzed Asymmetric Conjugate Addition Reaction

Zheng Ling, Fang Xie, Ilya D. Gridnev, Wanbin Zhang

SCI - Chemistry

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

3 Citations (Scopus)

Abstract

Significant solvent effects on enantioselection exist in the reaction of Cu-catalyzed asymmetric conjugate addition of alkylzinc reagents to α,β-unsaturated carbonyl compounds. Results of our DFT study suggest that solvent effects on enantioselection can be caused by structural changes in the stereodetermining Transition States (TS). We have seen how unconventional hydrogen bonding of the nucleophilic solvent results in a change of the computed optical yield comparable to that caused by well-known coordination of the solvent to the electrophilic metal center.

Original language	English
Pages (from-to)	346-351
Number of pages	6
Journal	Journal of the Chinese Chemical Society
Volume	65
Issue number	3
DOIs	https://doi.org/10.1002/jccs.201700263
Publication status	Published - 2018 Mar

Keywords

Asymmetric catalysis
Conjugate addition
DFT calculations
Solvent effects

ASJC Scopus subject areas

Chemistry(all)

Access to Document

10.1002/jccs.201700263

Cite this

@article{06c4cd6832764f35b0660d073a46863a,

title = "DFT Study of the Strong Solvent Effects in the Cu-Catalyzed Asymmetric Conjugate Addition Reaction",

abstract = "Significant solvent effects on enantioselection exist in the reaction of Cu-catalyzed asymmetric conjugate addition of alkylzinc reagents to α,β-unsaturated carbonyl compounds. Results of our DFT study suggest that solvent effects on enantioselection can be caused by structural changes in the stereodetermining Transition States (TS). We have seen how unconventional hydrogen bonding of the nucleophilic solvent results in a change of the computed optical yield comparable to that caused by well-known coordination of the solvent to the electrophilic metal center.",

keywords = "Asymmetric catalysis, Conjugate addition, DFT calculations, Solvent effects",

author = "Zheng Ling and Fang Xie and Gridnev, {Ilya D.} and Wanbin Zhang",

note = "Funding Information: This work was supported by the National Natural Science Foundation of China (Nos 21572129 and 21620102003), CAMPUS Asia Program of Tohoku University, and the High Performance Computing Center of Shanghai Jiao Tong University. Publisher Copyright: {\textcopyright} 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2018",

month = mar,

doi = "10.1002/jccs.201700263",

language = "English",

volume = "65",

pages = "346--351",

journal = "Journal of the Chinese Chemical Society",

issn = "0009-4536",

publisher = "Chinese Chemical Society",

number = "3",

}

TY - JOUR

T1 - DFT Study of the Strong Solvent Effects in the Cu-Catalyzed Asymmetric Conjugate Addition Reaction

AU - Ling, Zheng

AU - Xie, Fang

AU - Gridnev, Ilya D.

AU - Zhang, Wanbin

N1 - Funding Information: This work was supported by the National Natural Science Foundation of China (Nos 21572129 and 21620102003), CAMPUS Asia Program of Tohoku University, and the High Performance Computing Center of Shanghai Jiao Tong University. Publisher Copyright: © 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/3

Y1 - 2018/3

N2 - Significant solvent effects on enantioselection exist in the reaction of Cu-catalyzed asymmetric conjugate addition of alkylzinc reagents to α,β-unsaturated carbonyl compounds. Results of our DFT study suggest that solvent effects on enantioselection can be caused by structural changes in the stereodetermining Transition States (TS). We have seen how unconventional hydrogen bonding of the nucleophilic solvent results in a change of the computed optical yield comparable to that caused by well-known coordination of the solvent to the electrophilic metal center.

AB - Significant solvent effects on enantioselection exist in the reaction of Cu-catalyzed asymmetric conjugate addition of alkylzinc reagents to α,β-unsaturated carbonyl compounds. Results of our DFT study suggest that solvent effects on enantioselection can be caused by structural changes in the stereodetermining Transition States (TS). We have seen how unconventional hydrogen bonding of the nucleophilic solvent results in a change of the computed optical yield comparable to that caused by well-known coordination of the solvent to the electrophilic metal center.

KW - Asymmetric catalysis

KW - Conjugate addition

KW - DFT calculations

KW - Solvent effects

UR - http://www.scopus.com/inward/record.url?scp=85035218050&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85035218050&partnerID=8YFLogxK

U2 - 10.1002/jccs.201700263

DO - 10.1002/jccs.201700263

M3 - Article

AN - SCOPUS:85035218050

SN - 0009-4536

VL - 65

SP - 346

EP - 351

JO - Journal of the Chinese Chemical Society

JF - Journal of the Chinese Chemical Society

IS - 3

ER -

DFT Study of the Strong Solvent Effects in the Cu-Catalyzed Asymmetric Conjugate Addition Reaction

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this