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Title
Japanese:Rhodium-catalyzed enantioselective cyclizations of ﾎｳ-alkynylaldehydes with acyl phosphonates: ligand- and substituent-controlled C-P or C-H bond cleavage. 
English:Rhodium-catalyzed enantioselective cyclizations of ﾎｳ-alkynylaldehydes with acyl phosphonates: ligand- and substituent-controlled C-P or C-H bond cleavage. 
Author
Japanese: Kengo Masuda, Norifumi Sakiyama, Rie Tanaka, Keiichi Noguchi, Ken. Tanaka.  
English: Kengo Masuda, Norifumi Sakiyama, Rie Tanaka, Keiichi Noguchi, Ken. Tanaka.  
Language English 
Journal/Book name
Japanese:Journal of the American Chemical Society 
English:Journal of the American Chemical Society 
Volume, Number, Page Vol. 133    No. 18    pp. 6918-6921
Published date 2011 
Publisher
Japanese:American Chemical Society 
English:American Chemical Society 
Conference name
Japanese: 
English: 
Conference site
Japanese: 
English: 
DOI https://doi.org/10.1021/ja201337x
Abstract N-Propargyl 2-aminoacetaldehydes R1C竕｡CCH2NTsCH2CHO undergo cyclization with P-benzoylphosphonates ArCOP(O)(OR2)2 with either C-P- or C-H-bond cleavage, yielding 1-tosylpyrrolidines I and II, resp. (R1 = Me, Bu, Et, Ph; R2 = iPr, Et, Me; Ar = Ph, 2-MeC6H4, 4-ClC6H4, 4-FC6H4, 4-MeOC6H4, Me, Et, iPr), in dependence on catalyst and substrate. Cationic rhodium(I)/(R)-H8-BINAP or (R)-Segphos complexes catalyze the cycloaddn., the H8-BINAP favoring C-P-cleavage and formation of I with high yields and >99% ee and Segphos favoring C-H-bond cleavage with formation of II. The substituents of both ﾎｳ-alkynylaldehydes and acyl phosphonates also control the chemoselectivity of the cyclization. [on SciFinder(R)]

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