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γ‐Functionalisation of the 1‐Phosphanorbornadiene Structure
Author(s) -
Robin Frédéric,
Mercier François,
Ricard Louis,
Mathey François
Publication year - 1999
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/(sici)1099-0690(199905)1999:5<1091::aid-ejoc1091>3.0.co;2-1
Subject(s) - chemistry , carbanion , substituent , nucleophile , methylene , medicinal chemistry , base (topology) , group (periodic table) , stereochemistry , organic chemistry , catalysis , mathematical analysis , mathematics
Abstract 3‐Methyl‐substituted 1‐phosphanorbornadiene oxides or sulfides such as 1a,b are either metalated by a strong base ( n ‐BuLi or LDA) or brominated by NBS at the methyl substituent. The reaction of the resulting delocalised carbanions 2a,b takes place either at C‐2 (H + , MeI) or at the methylene group (Me 3 SiCl, ClPPh 2 , I 2 ). In the last case, γ‐functional ( 5a,b or 6a,b ) or bridged ( 7 ) phosphanorbornadienes are obtained. Similarly, the reaction of 3‐bromomethyl‐1‐phosphanorbornadiene oxides such as 8 with nucleophiles [NaCH(CO 2 Me) 2 , PhO – , Me 2 NH, PhCH 2 NH 2 ] yields the corresponding γ‐functional phosphanorbornadienes 9–12 . This chemistry has also been applied to the BIPNOR dioxide 13 .