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Catalytic Dicyanative 5‐ exo‐ and 6‐ endo ‐Cyclization Triggered by Cyanopalladation of Alkynes
Author(s) -
Arai Shigeru,
Koike Yuka,
Nishida Atsushi
Publication year - 2010
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.200900813
Subject(s) - chemistry , stereoselectivity , catalysis , triple bond , radical cyclization , combinatorial chemistry , stereochemistry , medicinal chemistry , double bond , organic chemistry
A stereoselective dicyanative 5‐ exo‐ and 6‐ endo ‐cyclization using various enynes has been investigated. The mode of cyclization is critically controlled by the structure of the substrates. For example, N ‐allyl derivatives prefer 5‐ exo ‐cyclization, while methacryloyl amides are transformed to the corresponding lactams with tetra ‐substituted carbons at the alpha‐position via 6‐ endo ‐cyclization. Both reactions include syn ‐cyanopalladation to carboncarbon triple bonds in the initial step, and sequential cyclization followed by reductive elimination in one operation enables the construction of the highly functionalized nitrogen heterocycles. The scope of suitable substrates and a proposed mechanism are also described.