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Cadmium(II) Chloride‐Catalyzed Dehydrative C−P Coupling of Propargyl Alcohols with Diarylphosphine Oxides to Afford Allenylphosphine Oxides
Author(s) -
Yang Jianlin,
Zhang Ming,
Qiu Kang,
Wang Lize,
Yu Jingjing,
Xia Zefeng,
Shen Ruwei,
Han LiBiao
Publication year - 2017
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201700957
Subject(s) - chemistry , propargyl , propargyl alcohol , medicinal chemistry , nucleophile , acetonitrile , steric effects , catalysis , triple bond , alcohol , sigmatropic reaction , nucleophilic substitution , organic chemistry , double bond
The cadmium(II) chloride‐catalyzed dehydrative C−P cross‐coupling reaction of propargyl alcohols with diarylphosphine oxides is reported. Several propargyl alcohols including those bearing the sterically demanding tert ‐butyl group at the triple bond terminus can be used as good substrates in the reaction to produce the corresponding allenylphosphine oxides in good to high yields in acetonitrile at 100 °C. The reaction can also be easily scaled up to a gram‐scale synthesis. A mechanism study indicates that the reaction may proceed through a process of propargylic substitution to generate phosphonite intermediates followed by [2,3] sigmatropic rearrangement to produce the allenyl products, rather than through a common allenylative substitution resulting from P‐nucleophilicity.