Palladacycle mediated synthesis of cyano-functionalized chiral 1,2-diphosphine and subsequent functional group transformations |
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Authors: | Mingjun Yuan |
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Institution: | Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore |
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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. |
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Keywords: | Allylic phosphine Asymmetric hydrophosphination Chiral diphosphine Palladacycle |
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