Premium
Regioselective Asymmetric Allylic Alkylation Reaction of α ‐Cyanoacetates Catalyzed by a Heterobimetallic Platina‐/Palladacycle
Author(s) -
Weiss Marcel,
Holz Julia,
Peters René
Publication year - 2016
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/ejoc.201501290
Subject(s) - chemistry , regioselectivity , stereocenter , allylic rearrangement , tsuji–trost reaction , nucleophile , catalysis , medicinal chemistry , palladium , substitution reaction , selectivity , oxidative addition , nucleophilic substitution , metal , stereochemistry , combinatorial chemistry , enantioselective synthesis , organic chemistry
Allylic substitution reactions provide a valuable tool for the functionalization of CH acidic pronucleophiles. Often, control over the stereocenter generated at the nucleophilic reactant is still a challenge. The majority of studies that address this issue employ metal complexes with a low metal oxidation state (e.g. Pd 0 ) to form allyl complexes through oxidative addition. In this article we describe the use of heterobimetallic Pt II /Pd II complexes, which probably activate the olefinic substrates through an S N 2′ pathway. The reaction of α‐cyanoacetates delivers linear allylation products with exclusive regioselectivity and high E / Z ‐selectivity for the new C=C double bond. Although the enantioselectivities attained are moderate, they are significantly higher than with related mono‐Pd II or ‐Pt II catalysts or the corresponding bis‐Pd II complex, which indicates cooperation of the different metals. Control experiments suggest simultaneous activation of both reaction partners.