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Acetylene‐Substituted Phosphane Oxides: Building Blocks for Macrocycles
Author(s) -
van Assema Sander G. A.,
de Jong G. Bas,
Ehlers Andreas W.,
de Kanter Frans J. J.,
Schakel Marius,
Spek Anthony L.,
Lutz Martin,
Lammertsma Koop
Publication year - 2007
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.200600877
Subject(s) - chemistry , acetylene , reagent , ring (chemistry) , oxidative coupling of methane , medicinal chemistry , crystal structure , derivative (finance) , stereochemistry , polymer chemistry , organic chemistry , catalysis , financial economics , economics
Phosphorus‐based macrocycles with acetylenic scaffolds have been built from acetylene‐substituted phosphane oxides that were formed from diisopropylphosphoramidic dibromide ( 3 ) and an acetylenic Grignard reagent. The four‐ and six‐edged macrocycles 15 and 16 , in which the i Pr 2 NP(O) units are connected through 1,3‐butadiyne rods, were obtained from the monosilylated derivative of i Pr 2 NP(O)(C 2 H) 2 ( 7 ) by multiple acetylene coupling reactions under oxidative Hay conditions. Reaction of i Pr 2 NP(O)(Br) 2 ( 3 ) with lithiated 1,2‐diethynylbenzene gave a mixture of cis and trans monocyclic bis(phosphane oxide) 18 . An X‐ray crystal structure determination of the trans isomer shows the ring structure to adopt a puckered form.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)