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Synthesis 2007(11): 1717-1723  
DOI: 10.1055/s-2007-966066
PAPER
© Georg Thieme Verlag Stuttgart · New York

P,N-Bidentate Phosphites with a Chiral Ketimine Fragment, Their Appli­cation in Enantioselective Allylic Substitution and Comparison with Phosphine­ Analogues

Konstantin Gavrilova, Vasily Tsarev*b, Sergey Zheglova, Alexander Korlyukovb, Mikhail Antipinb, Vadim Davankovb
a Department of Chemistry, Ryazan State Pedagogic University, 46 Svoboda str., Ryazan 390000, Russian Federation
Fax: +7(491)2775498; e-Mail: chem@ttc.ryazan.ru;
b Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova str., Moscow 119991, Russian Federation
Fax: +7(495)1356471; e-Mail: tsarev@ineos.ac.ru;
Further Information

Publication History

Received 19 December 2006
Publication Date:
11 May 2007 (online)

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Abstract

Novel chiral P,N-bidentate arylphosphites have been prepared by a one-step phosphorylation of appropriate hydroxy ketimines based on (R)-(+)-camphor. Metal chelate complexes [Rh(CO)(PN)Cl] and [Pd(PN)(allyl)]BF4 with the ligands were obtained and the new compounds were fully characterized by 1H, 13C and 31P NMR, IR, MS (EI, FAB and ESI techniques) and X-ray crystal structure analysis. Using these ligands, up to 73% ee has been achieved in the asymmetric palladium-catalyzed sulfonylation of 1,3-diphenyl-2-propenyl acetate with sodium p-toluenesulfinate. In the enantioselective alkylation of the same substrate with di­methyl malonate, up to 94% enantioselectivity has been achieved.

Key words

allylations - asymmetric catalysis - chiral ketimines - palladium - P,N-ligands

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Sheldrick G. M. SADABS, v 2.01, Bruker/Siemens Area Detector Absorption Correction Program, Bruker AXS, Madison, Wisconsin, USA