Synthesis of 1,5- P, N-phosphino-sulfoximines through phospha-Michael reaction of alkenyl sulfoximines and their evaluation as ligands in palladium-catalyzed allylic alkylation

We describe a modular synthesis of cyclic and acyclic 1,5- P, N-phosphino-sulfoximines by using a phospha-Michael reaction of the corresponding alkenyl sulfoximines with HPPh 2/KO tBu as key step, which proceeds with medium diastereoselectivity. The palladium-catalyzed allylic alkylation of racemic...

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Bibliographic Details
Published inTetrahedron letters Vol. 48; no. 49; pp. 8752 - 8756
Main Authors Lemasson, Fabien, Gais, Hans-Joachim, Raabe, Gerhardt
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 03.12.2007
Elsevier
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
ALCOHOLS
SULFOXIDES
ASYMMETRIC-SYNTHESIS
CARBONATES
KINETIC RESOLUTION
AMINOSULFOXONIUM YLIDES
COMPLEXES
CHEMISTRY
SULFUR
ENANTIOSELECTIVE SUBSTITUTION
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Summary:We describe a modular synthesis of cyclic and acyclic 1,5- P, N-phosphino-sulfoximines by using a phospha-Michael reaction of the corresponding alkenyl sulfoximines with HPPh 2/KO tBu as key step, which proceeds with medium diastereoselectivity. The palladium-catalyzed allylic alkylation of racemic 1,3-diphenyl allyl acetate with malonate in the presence of a S S R C R C-configured N-benzyl-substituted cyclic phosphino-sulfoximine gave the corresponding alkene with 97% ee in 98% yield. A comparative study of N-substituted phosphino-sulfoximines showed the selectivity of the Pd(0)-catalyst to be dependent not only on the chiral backbone of the ligand but also on the N-substituent and configuration of the sulfoximine group.
ISSN:0040-4039
1873-3581
DOI:10.1016/j.tetlet.2007.10.006