Premium
Regio‐ and Stereoselective Nucleophilic Substitutions of Chiral Allylic Alcohol Rhenium Complexes
Author(s) -
Legoupy Stéphanie,
Crévisy Christophe,
Guillemin JeanClaude,
Grée René,
Toupet Loic
Publication year - 1998
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/(sici)1521-3765(19981102)4:11<2162::aid-chem2162>3.0.co;2-y
Subject(s) - allylic rearrangement , chemistry , regioselectivity , rhenium , medicinal chemistry , nucleophile , alcohol , stereospecificity , substitution reaction , nucleophilic substitution , stereoselectivity , stereochemistry , organic chemistry , catalysis
The nucleophilic substitution by alcohols, thiols, allyl silane, or triphenylphosphane of the hydroxy group of an allylic alcohol complexed to a chiral rhenium salt leads to the corresponding ethers, thioethers, 1,5‐dienes, and phosphonium salts in high yields [Eq. (1)]. The high regioselectivity of these reactions was unambiguously established by means of a deuterated ligand or with substituted allylic alcohols and any allylic rearrangement reaction was excluded. The reaction of the separate diastereoisomeric rhenium complexes derived from 3‐buten‐2‐ol established that this substitution is stereospecific with overall retention of configuration. Nu = OR, SR, + PPh 3 [BF 4 ] − , CH 2 CHCH 2 , OAc; R, R′ = H, H; H, CH 3 ; CH 3 , H.