Abstract

Abstract The asymmetric synthesis of phosphinous compounds from diheterophosphacycloal kane-1,3,2 was investigated in a transition metal complex series. Complexes 1 and 2 were prepared from diaminophosphine, (−)-ephedrine and W (CO)5 THP (1: δ31 P=+147,6 ppm; JPW=313 Hz M.+=595;2 δ3 p=+156 ppm JPW=304 Hz M.+=533; 90%dp) in two steps. Methyl lithium reacted with 1 to give stereospecific 3 (83%Yield) by P-O linkage (3 δ31 P=+64 ppm; JPW =261 Hz; M.+ − 28=583). The aminophosphine complex 3 was stereochemically stable and was used for studies of synthetic applications. HCL gas reacted with 3 in CH2Cl2 to give the non optically active chlorophosphine complex 4 (δ31 P=+103,6 ppm; JPW=290 Hz; M.+ =482). This compound immediately gave salt 6 (δ31 P=+66,7 ppm; JPW =240 Hz) by reaction with (−)-menthol and triethylamine. The acid methanolysis of 3 gave a mixture of 5 and 6 and the unchanged (−)-ephedrine salt [5:30% yield; δ31 P=+114 ppm; Jpw=280 Hz; [α]D=+1,2° (CH2Cl2); M.+=478; 6 : 60% yield; δ31p=+102,9 ppm; JPW...

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