The Lithiation Reactivity and Selectivity of Differentially Branched Alkyldiphenylphosphine Oxides - A Simple and Versatile Approach to ortho-Functionalized Arylphosphine Oxides

0443900 - ÚOCHB 2016 RIV DE eng J - Článek v odborném periodiku
Mahamulkar, Shraddha G. - Císařová, I. - Jahn, Ullrich
The Lithiation Reactivity and Selectivity of Differentially Branched Alkyldiphenylphosphine Oxides - A Simple and Versatile Approach to ortho-Functionalized Arylphosphine Oxides.
Advanced Synthesis & Catalysis. Roč. 357, č. 4 (2015), s. 793-799. ISSN 1615-4150. E-ISSN 1615-4169
Grant CEP: GA ČR GAP207/11/1598
Institucionální podpora: RVO:61388963
Klíčová slova: lithiation * nucleophilic substitution * organolithium reagents * phosphine oxides * phosphine-borane complexes
Kód oboru RIV: CC - Organická chemie
Impakt faktor: 6.453, rok: 2015

Alkyldiphenylphosphine oxides typically undergo alpha-deprotonation with alkyllithium reagents. Here, the lithiation of differentially branched alkyl-diphenylphosphine oxides was investigated and a diverse, but predictable reactivity was found. gamma-Branched derivatives undergo selective directed ortho-metalation (DoM) using butyllithium and TMEDA as an additive. With decreasing degree of gamma-branching alpha-lithiation becomes predominant. The ortho-phosphinoyllithium intermediates are subject to functionalization and C-C 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.
Trvalý link: http://hdl.handle.net/11104/0246567