Asymmetric ligand transformation reactions

Abstract

The organopalladium complex containing ortho-metalated (R)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary has been used to promote the asymmetric [4+2] Diels-Alder reaction between the cyclic dienes, 3,4-dimethyl-1-phenylphosphole and 3,4-dimethyl-1-phenylphosphole-1-sulfide with sulfonated and non-sulfonated phosphine and arsine functionalized dienophiles viz., diphenylvinylphosphine sulfide, divinylphenylphosphine sulfide, divinylphenylphosphine, diphenylvinylarsine and divinylphenylarsine. The platinum analogue of the complex was also employed to promote the asymmetric Diels-Alder reaction between 3,4-dimethyl-1-phenylphosphole and phosphine functionalized terminal alkenols, 3-diphenylphosphanyl-but-3-en-1-ol and 2-diphenylphosphanyl-prop-2-en-1-ol, culminating in the synthesis of P-chiral phosphanorbornene systems with hydroxyl functionality. The chiral templates were also utilized for hydrophosphination of the aforementioned alkenols thereby yielding diphosphines with chirality residing on the carbon backbone.