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Palladium‐Catalyzed Arylation of a Sterically Demanding gem ‐Dibromophosphaethene
Author(s) -
Ito Shigekazu,
Shinozaki Tomokazu,
Mikami Koichi
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201601105
Subject(s) - palladium , chemistry , aryl , synthon , phosphine , bromide , catalysis , medicinal chemistry , steric effects , halogen , bromine , combinatorial chemistry , ligand (biochemistry) , organic chemistry , alkyl , biochemistry , receptor
Abstract The trans bromide of 2,2‐dibromo‐1‐(2,4,6‐tri‐ t ‐butylphenyl)‐1‐phosphaethene (Mes*P=CBr 2 ; Mes*=2,4,6‐ t Bu 3 C 6 H 2 ) can be successfully substituted with an aryl group by using a palladium version of the Kumada‐Tamao‐Corriu cross‐coupling process. Predominant formation of the 2‐aryl‐2‐bromo‐1‐phosphaethene [( Z )‐Mes*P=C(Br)Ar] required suitable conditions including optimization of the ancillary phosphine ligand, thereby retarding the dual elimination of bromides leading to phosphaalkyne (Mes*C≡P). The 2‐aryl‐2‐bromo‐1‐phosphaethenes hold promise as versatile synthons for functional π‐conjugated molecules, and stereospecific transformations of the bromine atom by halogen‐metal exchange and palladium‐catalyzed arylations were demonstrated.