A Transient Vinylphosphinidene via a Phosphirene-Phosphinidene Rearrangement

Liu Leo Liu; Jiliang Zhou; Levy L. Cao; Ryan Andrews; Rosalyn L. Falconer; Christopher A. Russell; Douglas W. Stephan

doi:10.1021/jacs.7b11791

A Transient Vinylphosphinidene via a Phosphirene-Phosphinidene Rearrangement

Liu Leo Liu, Jiliang Zhou, Levy L. Cao, Ryan Andrews, Rosalyn L. Falconer, Christopher A. Russell, Douglas W. Stephan^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

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Abstract

A room-temperature-stable crystalline 2H-phosphirene (1) was prepared by treatment of an electrophilic diamidocarbene with tert-butylphosphaalkyne. Compound 1 is shown to react as a vinylphosphinidene generated via phosphirene-phosphinidene rearrangement. Thermolysis is shown to affect C-N bond scission while reactions with C₆Cl₄O₂ or (tht)AuCl afford formal oxidation of the phosphindene center and the phosphinidene-insertion into an aromatic C-C bond of a mesityl group, respectively. The latter reaction is the first example of a phosphorus analog of the Büchner ring expansion reaction.

Original language	English
Pages (from-to)	147-150
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	140
Issue number	1
Early online date	22 Dec 2017
DOIs	https://doi.org/10.1021/jacs.7b11791
Publication status	Published - 10 Jan 2018

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title = "A Transient Vinylphosphinidene via a Phosphirene-Phosphinidene Rearrangement",

abstract = "A room-temperature-stable crystalline 2H-phosphirene (1) was prepared by treatment of an electrophilic diamidocarbene with tert-butylphosphaalkyne. Compound 1 is shown to react as a vinylphosphinidene generated via phosphirene-phosphinidene rearrangement. Thermolysis is shown to affect C-N bond scission while reactions with C6Cl4O2 or (tht)AuCl afford formal oxidation of the phosphindene center and the phosphinidene-insertion into an aromatic C-C bond of a mesityl group, respectively. The latter reaction is the first example of a phosphorus analog of the B{\"u}chner ring expansion reaction.",

author = "Liu, {Liu Leo} and Jiliang Zhou and Cao, {Levy L.} and Ryan Andrews and Falconer, {Rosalyn L.} and Russell, {Christopher A.} and Stephan, {Douglas W.}",

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T1 - A Transient Vinylphosphinidene via a Phosphirene-Phosphinidene Rearrangement

AU - Liu, Liu Leo

AU - Zhou, Jiliang

AU - Cao, Levy L.

AU - Andrews, Ryan

AU - Falconer, Rosalyn L.

AU - Russell, Christopher A.

AU - Stephan, Douglas W.

PY - 2018/1/10

Y1 - 2018/1/10

N2 - A room-temperature-stable crystalline 2H-phosphirene (1) was prepared by treatment of an electrophilic diamidocarbene with tert-butylphosphaalkyne. Compound 1 is shown to react as a vinylphosphinidene generated via phosphirene-phosphinidene rearrangement. Thermolysis is shown to affect C-N bond scission while reactions with C6Cl4O2 or (tht)AuCl afford formal oxidation of the phosphindene center and the phosphinidene-insertion into an aromatic C-C bond of a mesityl group, respectively. The latter reaction is the first example of a phosphorus analog of the Büchner ring expansion reaction.

AB - A room-temperature-stable crystalline 2H-phosphirene (1) was prepared by treatment of an electrophilic diamidocarbene with tert-butylphosphaalkyne. Compound 1 is shown to react as a vinylphosphinidene generated via phosphirene-phosphinidene rearrangement. Thermolysis is shown to affect C-N bond scission while reactions with C6Cl4O2 or (tht)AuCl afford formal oxidation of the phosphindene center and the phosphinidene-insertion into an aromatic C-C bond of a mesityl group, respectively. The latter reaction is the first example of a phosphorus analog of the Büchner ring expansion reaction.

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A Transient Vinylphosphinidene via a Phosphirene-Phosphinidene Rearrangement

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A Transient Vinylphosphinidene via a Phosphirene-Phosphinidene Rearrangement

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