Myrtanyl-, bornyl- and isopinocampheyldichlorophosphines have been prepared from the corresponding alkyl chlorides via diastereospecific reactions of the Grignard reagents with PCl(3) or (Et(2)N)(2)PCl. Two applications of these compounds to synthetic asymmetric organophosphorus chemistry have been examined: their reactions with 2,3,3-trimethylbutene and AlCl(3) afford either P-chiral phosphetane oxides or, in the presence of gaseous HCl, P-chiral phosphinic chlorides with moderate to high diastereoselectivity.
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