1. Palladacycle mediated synthesis of cyano-functionalized chiral 1,2-diphosphine and subsequent functional group transformations
- Author
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Yuan, Mingjun, Pullarkat, Sumod A., Li, Yongxin, and Leung, Pak-Hing
- Subjects
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INORGANIC synthesis , *CHIRALITY , *PHOSPHINE , *FUNCTIONAL groups , *ALDEHYDES , *CHEMICAL reactions , *COMPLEX compounds , *ASYMMETRY (Chemistry) , *X-ray crystallography - Abstract
Abstract: Cyano-functionalized allylic phosphine substrates containing the ortho-metalated (R)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary were synthesized from bromoacetaldehyde dimethylacetal via a one-pot process. The diastereoselective hydrophosphination reactions of the cis- and trans-allylic phosphine substrates gave the cyano-functionalized chiral 1,2-bis(diphenylphosphino)ethane products with high yield and stereoselectivity. The subsequent organic transformation reactions of the cyano-substituted products chemoselectively afforded the formyl- and hydroxyl-functionalized chiral 1,2-diphosphine complexes with retention of stereochemistry. The coordination properties and absolute configurations of the novel 1,2-diphosphine complexes were established by single crystal X-ray crystallography. The optically pure 1,2-bis(diphenylphosphino)ethane ligands with cyano-, formyl- and hydroxyl-functionalities could be liberated in high yields from the corresponding dihalo palladium complexes by treatment with aqueous potassium cyanide. [Copyright &y& Elsevier]
- Published
- 2011
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