کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1324770 | 977354 | 2011 | 8 صفحه PDF | دانلود رایگان |
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.
Cyano-functionalized allylic monophosphine substrates were synthesized from bromoacetaldehyde dimethylacetal via a one-pot process. Subsequent hydrophosphination and the functional group transformation reactions generated the cyano-, formyl- and hydroxyl-functionalized chiral 1,2-diphosphine products in high yields and stereoselectivity.Figure optionsDownload as PowerPoint slideResearch highlights
► One-pot synthesis of Cyano-functionalized allylic monophosphine.
► Asymmetric hydrophosphination of the allylic monophosphine substrates.
► Novel functional group transformations of cyano-functionalized 1,2-diphosphines.
► Access to a range of enantiomerically pure functionalized 1,2-diphopshine ligands.
Journal: Journal of Organometallic Chemistry - Volume 696, Issue 4, 15 February 2011, Pages 905–912