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Aromatic Osmacyclopropenefuran Bicycles and Their Relevance for the Metal‐Mediated Hydration of Functionalized Allenes
Author(s) -
Batuecas María,
CastroRodrigo Ruth,
Esteruelas Miguel A.,
GarcíaYebra Cristina,
López Ana M.,
Oñate Enrique
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201606839
Subject(s) - relevance (law) , metal , chemistry , organic chemistry , political science , law
The aromatic osmacyclopropenefuran bicycles [OsTp{κ 3 ‐C 1 ,C 2 ,O‐(C 1 H 2 C 2 CHC(OEt)O)}(P i Pr 3 )]BF 4 (Tp=hydridotris(1‐pyrazolyl)borate) and [OsH{κ 3 ‐C 1 ,C 2 ,O‐(C 1 H 2 C 2 CHC(OEt)O)}(CO)(P i Pr 3 ) 2 ]BF 4 , with the metal fragment in a common vertex between the fused three‐ and five‐membered rings, have been prepared via the π‐allene intermediates [OsTp(η 2 ‐CH 2 =CCHCO 2 Et)(OCMe 2 )(P i Pr 3 )]BF 4 and [OsH(η 2 ‐CH 2 =CCHCO 2 Et)(CO)(OH 2 )(P i Pr 3 ) 2 ]BF 4 , and their aromaticity analyzed by DFT calculations. The bicycle containing the [OsH(CO)(P i Pr 3 ) 2 ] + metal fragment is a key intermediate in the [OsH(CO)(OH 2 ) 2 (P i Pr 3 ) 2 ]BF 4 ‐catalyzed regioselective anti‐Markovnikov hydration of ethyl buta‐2,3‐dienoate to ethyl 4‐hydroxycrotonate.