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A New Catalytic Route to Boryl‐ and Borylsilyl‐Substituted Buta‐1,3‐dienes
Author(s) -
Walkowiak Jȩdrzej,
JankowskaWajda Magdalena,
Marciniec Bogdan
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800518
Subject(s) - alkyne , phenylacetylene , catalysis , chemistry , triple bond , medicinal chemistry , polymer chemistry , combinatorial chemistry , organic chemistry , double bond
Vinyl‐substituted boronates in the presence of complexes containing RuH bonds (preferably [Ru(CO)ClH(PCy 3 ) 2 ], Cy: cyclohexyl) react regioselectively with terminal ethynes (involving silylethynes), albeit with the exception of phenylacetylene, to produce boryl‐ and borylsilyl‐substituted buta‐1,3‐dienes with a preference for E , E ‐diene. The reaction opens a new catalytic route for the preparation of dienylboronates, and particularly dienylsilylboronates, that are functionalised building blocks in the synthesis of organic and natural products. The mechanism of this new reaction was proved to involve an insertion of alkyne into RuH bonds followed by an insertion of coordinated vinyl boronate into the RuC bond and β‐hydrogen transfer to the metal to eliminate boryldiene or borylsilyldiene.