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The Lithiation Reactivity and Selectivity of Differentially Branched Alkyldiphenylphosphine Oxides – A Simple and Versatile Approach to ortho‐ Functionalized Arylphosphine Oxides
Author(s) -
Mahamulkar Shraddha G.,
Císařová Ivana,
Jahn Ullrich
Publication year - 2015
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201400861
Subject(s) - chemistry , metalation , deprotonation , borane , reactivity (psychology) , phosphine , reagent , combinatorial chemistry , catalysis , surface modification , selectivity , organic chemistry , medicine , ion , alternative medicine , pathology
Alkyldiphenylphosphine oxides typically undergo α‐deprotonation with alkyllithium reagents. Here, the lithiation of differentially branched alkyldiphenylphosphine oxides was investigated and a diverse, but predictable reactivity was found. γ‐Branched derivatives undergo selective directed ortho ‐metalation (DoM) using butyllithium and TMEDA as an additive. With decreasing degree of γ‐branching α‐lithiation becomes predominant. The ortho ‐phosphinoyllithium intermediates are subject to functionalization and CC bond forming reactions, thus providing a convenient approach to new phosphine oxides and phosphine‐borane complexes, which have a good potential for an approach to new ligands for catalysis.