Edwards, Peter Gerald  ORCID: https://orcid.org/0000-0001-6999-753X, Knight, James Christopher and Newman, Paul David ORCID: https://orcid.org/0000-0002-1808-1211
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
|
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: | Schools > Chemistry Research Institutes & Centres > Cardiff Catalysis Institute (CCI) |
| Subjects: | Q Science > QD Chemistry |
| Publisher: | RSC |
| ISSN: | 1477-9226 |
| Last Modified: | 18 Oct 2022 13:08 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/12447 |
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