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Synthesis of (1R,4S,6R)-5,5,6-trimethyl-2-phosphabicyclo[2.2.2]octane and derivatives

Edwards, Peter Gerald, Knight, James Christopher and Newman, Paul David 2010. Synthesis of (1R,4S,6R)-5,5,6-trimethyl-2-phosphabicyclo[2.2.2]octane and derivatives. Dalton Transactions 39 (16) , pp. 3851-3860. 10.1039/b924983d

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Abstract

The novel primary phosphine (1R,3S)-[1,2,2-trimethyl-3-(phosphinomethyl)cyclopentyl]methyl methanesulfonate 3a (or tosylate 3b) has been prepared in three steps from (1R,3S)-camphoric acid with a view to utilising it as a synthon for the preparation of polycyclic phosphines. Efforts to prepare a [3.2.1] bicyclic product by internal cyclisation of 3a or 3b under various conditions were unsuccessful, but heating the neat compound at 140 °C for several hours gave the new asymmetric, bicyclic secondary phosphine, (1R,4S,6R)-5,5,6-trimethyl-2-phosphabicyclo[2.2.2]octane (PBO) as its methanesulfonic acid 5a (or p-toluenesulfonic acid 5b) salt. The cyclisation involves a skeletal rearrangement and occurs with high stereoselectivity to generate two new stereogenic carbon centres and a chiral phosphorus atom. The secondary phosphine was obtained after base treatment of 5a/b and several derivatives of the phosphine have been synthesised and characterised. Reaction of two mol equivalents of the borane adduct of PBO with α,α′-dichloro-ortho-xylene gave the bidentate derivative, o-C6H4(CH2PBO)2.2BH3, 12, and ultimately o-C6H4(CH2PBO)2, 13. Complexes of 13 with Pd(II), Pt(II), Pt(0) and Mo(0) have been prepared and characterised by spectroscopic and analytical methods including single-crystal X-ray structure determinations of cis-Pd{o-C6H4(CH2PBO)2}Cl2, 14, cis-Pt{o-C6H4(CH2PBO)2}Cl2, 15 and Mo(CO)4{o-C6H4(CH2PBO)2} 17.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Subjects: Q Science > QD Chemistry
Publisher: RSC
ISSN: 1477-9226
Last Modified: 04 Jun 2017 02:49
URI: http://orca.cf.ac.uk/id/eprint/12447

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