کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1325568 | 1499880 | 2014 | 6 صفحه PDF | دانلود رایگان |
• Metalated tert-butanesulfinamides are good partners for Pd(0)-catalyzed allylic substitutions.
• Allylic substitution of linear allylic carbonates proceeds in the absence of base.
• The cross-coupling is totally regioselective and highly diastereoselective.
• The sulfur atom remains configurationally stable throughout the allylation process.
The performance of tert-butanesulfinamides as nitrogen nucleophiles in Pd(0)-catalyzed allylic substitution reactions has been investigated. Metalated N-alkyl and N-acetyl sulfinamides have been identified as suitable partners for the reaction with π-allyl–palladium complexes. The cross-coupling of N-acetyl tert-butanesulfinamide with 2- or 3-substituted linear allylic carbonates is achieved in the presence of Pd(OAc)2 (5 mol%) and dppe (7.5 mol%) and does not require an additional base. The reaction proceeds in high yields (59–98%) to produce the corresponding E-configured linear allylic sulfinamides in a totally regioselective and highly diastereoselective manner. The sulfur atom remains configurationally stable throughout the allylation process, and thus the coupling products are obtained in enantiomerically pure form.
Metalated N-alkyl and N-acetyl tert-butanesulfinamides have been identified as suitable partners for Pd(0)-catalyzed allylic substitution reactions. Significantly, the regio- and diastereoselective cross-coupling of N-acetyl tert-butanesulfinamide with linear allylic 2- or 3-substituted carbonates is achieved with a readily available catalyst and does not require the presence of an added base.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 760, 15 June 2014, Pages 124–129