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Efficient Isomerization of Allylic Alcohols to Saturated Carbonyl Compounds by Activated Rhodium and Ruthenium Complexes
Author(s) -
Uma Ramalinga,
Davies Maxwell K.,
Crévisy Christophe,
Grée René
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200108)2001:16<3141::aid-ejoc3141>3.0.co;2-y
Subject(s) - isomerization , chemistry , allylic rearrangement , ruthenium , rhodium , medicinal chemistry , hydride , methanol , photochemistry , organic chemistry , catalysis , hydrogen
A range of readily available rhodium complexes of the general structures Rh(PPh 3 ) 3 + PF 6 − and RhX(PPh 3 ) 3 (X = H, Me, Ph) have been prepared and used in situ for the isomerization of allylic alcohols to their corresponding saturated carbonyl compounds. The isomerization of octen‐3‐ol, selected as a model, yielded octan‐3‐one in good yield. This reaction has been extended to the corresponding ruthenium complexes of the general structures [RuCl(PPh 3 ) 3 ] + PF 6 − , RuXCl(PPh 3 ) 3 and RuX 2 (PPh 3 ) 3 (X = H, Me, Ph). It is noteworthy that many of these complexes have not been employed previously for this isomerization. The scope and efficiency of the process has been demonstrated by four representative complexes [RhH(PPh 3 ) 3 , RuH 2 (PPh 3 ) 3 , RuPh 2 (PPh 3 ) 3 , RuCl(PPh 3 ) 3 + PF 6 − ] with a wide variety of allylic alcohols. The reaction of primary allylic alcohols in the presence of RuCl(PPh 3 ) 3 + PF 6 − in methanol yields aldehydes protected as their methyl acetals. Deuterium labelling experiments are in agreement with a 1,3‐hydride shift mechanism.