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Catalytic 1,2‐Dicyanation of Alkynes by Palladium(II) under Aerobic Conditions
Author(s) -
Arai Shigeru,
Sato Takashi,
Nishida Atsushi
Publication year - 2009
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.200900334
Subject(s) - chemistry , cyanation , propargyl , palladium , catalysis , trimethylsilyl cyanide , triple bond , medicinal chemistry , stereoselectivity , alkyne , cyanide , organic chemistry , double bond
A stereoselective 1,2‐dicyanation of various alkynes in the presence of trimethylsilyl cyanide (TMSCN) by palladium(II) catalysis under aerobic conditions is investigated. This reaction includes two cyanation pathways, syn ‐ and anti ‐cyanopalladation to alkynes that are activated by Pd(II). High syn ‐selectivity was observed in the reaction using terminal alkynes that have bulky substituents at a propargyl position and aliphatic internal alkynes. Furthermore, a dramatic acceleration was observed with substrates having an N ‐arenesulfonyl functionality at a propargyl position, this indicates that both sulfoxide and carbon‐carbon triple bond act as Lewis bases to Pd(II).