63.  "Synthesis, Reactivity, and Resolution of a C2–Symmetric, P–Stereogenic Benzodiphosphetane, a Building Block for Chiral Bis(phosphines)." Reynolds, S. C.; Hughes, R. P.; Glueck, D. S.; Rheingold, A. L. Org. Lett. 2012, 14, 4238–4241.
 
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Abstract

Although the pyramidal inversion barriers in diphosphines (R2P-PR2) are similar to those in phosphines (PR3), P-stereogenic chiral diphosphines have rarely been exploited as building blocks in asymmetric synthesis. The synthesis, reactivity, and resolution of the benzodiphosphetane trans-1,2-(P(t-Bu))2C6H4 are reported. Alkylation with MeOTf followed by addition of a nucleophile gave the useful C2-symmetric P-stereogenic ligand BenzP* and novel analogues.


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