Alkoxyphosphorane/Borane Cooperative Alkylations: A Frustrated Lewis Pair Version of the Mitsunobu Reaction

Ting Chen; Yanbo Mei; Liu Leo Liu; Yufen Zhao; Yile Wu; Douglas W Stephan

doi:10.1002/chem.202300264

Alkoxyphosphorane/Borane Cooperative Alkylations: A Frustrated Lewis Pair Version of the Mitsunobu Reaction

Chemistry. 2023 Apr 21;29(23):e202300264. doi: 10.1002/chem.202300264. Epub 2023 Mar 15.

Authors

Ting Chen¹, Yanbo Mei², Liu Leo Liu², Yufen Zhao¹, Yile Wu¹, Douglas W Stephan^{1

3}

Affiliations

¹ Institute of Drug Discovery Technology, Ningbo University, 315211, Ningbo, Zhejiang, P. R. China.
² Department of Chemistry and, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, 518055, Shenzhen, P. R. China.
³ Department of Chemistry, University of Toronto, 80 St. George St, M5S3H6, Toronto, ON, Canada.

PMID: 36715454
DOI: 10.1002/chem.202300264

Abstract

The combination of the alkoxyphosphoranes, Ph₂ P(OR)(O₂ C₆ Cl₄ ) and the borane B(C₆ F₅ )₃ generates the zwitterions 3 which act as FLP to effect the alkylation of several nucleophiles affording C-C, C-N, C-H and C-Cl coupling products. A DFT study shows the reaction proceeds via an FLP activation pathway generating an alkoxyphosphonium intermediate which effects the alkylation of the nucleophiles, akin to the Mitsunobu reaction.

Keywords: DFT calculations; P(V) chemistry; alkylations; frustrated Lewis pairs.

Abstract

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