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Rhodium‐Catalyzed Cascade Reaction of 1,6‐Enynes Involving Addition, Cyclization, and β‐Oxygen Elimination
Author(s) -
Miura Tomoya,
Shimada Masahiko,
Murakami Masahiro
Publication year - 2006
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200600254
Subject(s) - chemistry , allylic rearrangement , rhodium , enyne , moiety , nucleophile , double bond , triple bond , catalysis , regioselectivity , medicinal chemistry , allene , olefin fiber , cascade reaction , cyclopropanation , intramolecular force , organic chemistry
The reaction of arylboronic acids with 1,6‐enynes that contain an allylic ether moiety is catalyzed by a rhodium(I) complex to produce cyclopentanes with a tetrasubstituted exo olefin and a pendant vinyl group. The reaction is initiated by the regioselective addition of an arylrhodium(I) species to the carbon–carbon triple bond of the 1,6‐enyne. The resulting alkenylrhodium(I) compound subsequently undergoes intramolecular carborhodation of the allylic double bond in a 5‐ exo ‐trig mode. β Elimination of the methoxy group affords the cyclization product and the catalytically active methoxorhodium(I) species. The use of alkyl Grignard reagents instead of arylboronic acids as organometallic nucleophiles was also examined.