Soft propargylic deprotonation: Designed ligand enables au-catalyzed isomerization of alkynes to 1,3-Dienes

Zhixun Wang; Yanzhao Wang; Liming Zhang

doi:10.1021/ja503909c

Soft propargylic deprotonation: Designed ligand enables au-catalyzed isomerization of alkynes to 1,3-Dienes

Zhixun Wang, Yanzhao Wang, Liming Zhang

Chemistry (Twin Cities)

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

81 Scopus citations

Abstract

By functionalizing the privileged biphenyl-2-ylphosphine with a basic amino group at the rarely explored 3′ position, the derived gold(I) complex possesses orthogonally positioned "push" and "pull" forces, which enable for the first time soft propargylic deprotonation and permit the bridging of a difference of >26 pK_a units (in DMSO) between a propargylic hydrogen and a protonated tertiary aniline. The application of this design led to efficient isomerization of alkynes into versatile 1,3-dienes with synthetically useful scope under mild reaction conditions.

Original language	English (US)
Pages (from-to)	8887-8890
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	25
DOIs	https://doi.org/10.1021/ja503909c
State	Published - Jun 25 2014

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author = "Zhixun Wang and Yanzhao Wang and Liming Zhang",

year = "2014",

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doi = "10.1021/ja503909c",

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T2 - Designed ligand enables au-catalyzed isomerization of alkynes to 1,3-Dienes

AU - Wang, Zhixun

AU - Wang, Yanzhao

AU - Zhang, Liming

PY - 2014/6/25

Y1 - 2014/6/25

N2 - By functionalizing the privileged biphenyl-2-ylphosphine with a basic amino group at the rarely explored 3′ position, the derived gold(I) complex possesses orthogonally positioned "push" and "pull" forces, which enable for the first time soft propargylic deprotonation and permit the bridging of a difference of >26 pKa units (in DMSO) between a propargylic hydrogen and a protonated tertiary aniline. The application of this design led to efficient isomerization of alkynes into versatile 1,3-dienes with synthetically useful scope under mild reaction conditions.

AB - By functionalizing the privileged biphenyl-2-ylphosphine with a basic amino group at the rarely explored 3′ position, the derived gold(I) complex possesses orthogonally positioned "push" and "pull" forces, which enable for the first time soft propargylic deprotonation and permit the bridging of a difference of >26 pKa units (in DMSO) between a propargylic hydrogen and a protonated tertiary aniline. The application of this design led to efficient isomerization of alkynes into versatile 1,3-dienes with synthetically useful scope under mild reaction conditions.

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Soft propargylic deprotonation: Designed ligand enables au-catalyzed isomerization of alkynes to 1,3-Dienes

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