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

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Edwards, Peter G. Knight, James C. Newman, Paul D.
Description	Author Affiliation: Edwards PG ( School of Chemistry, Cardiff University, Cardiff, UK CF10 3AT. edwardspg@cardiff.ac.uk)
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 (1 R,3 S)-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 , (1 R,4 S,6 R)-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, $o-C_{6}H_{4}(CH_{2}PBO)_{2}.2BH_{3},$ 12, and ultimately $o-C_{6}H_{4}(CH_{2}PBO)_{2},$ 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 $cis-Pd\{o-C_{6}H_{4}(CH_{2}PBO)_{2}\}Cl_{2},$ 14, $cis-Pt\{o-C_{6}H_{4}(CH_{2}PBO)_{2}\}Cl_{2},$ 15 and $Mo(CO)_{4}\{o-C_{6}H_{4}(CH_{2}PBO)_{2}\}$ 17.
ISSN	14779226
Issue Number	16
Journal	Dalton Trans.
Volume Number	39
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2010-04-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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