Silicon tetrachloride mediated asymmetric aldol addition reaction

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2013
Tan, Duygu
Aldol addition reaction is one of the most important and most studied carbon-carbon bond forming reactions in organic chemistry. Recent studies focused on the catalytic version of this chemistry. Different from the classical Mukaiyama-type aldol reactions, chiral lewis bases have been used as promoters. In the presence of SiCl4, these reactions proceed through a cyclic transition state leading to anti aldol product as a major product with moderate-to-good diastereo and enantioselectivities. Phosphoramide derivatives, BINAPO, BINAPO derivatives, N,N-dioxides and N-oxides have been extensively used for this purpose. Recently, our group has designed new phosphine oxy aziridinyl phosphonates (POAP) as chiral Lewis bases. These promoters were used for the asymmetric aldol addition reaction between cyclohexanone and different aldehydes in the presence of SiCl4. Moreover, our previously designed phosphine oxy ferrocenyl substituted aziridinyl methanol (POFAM) ligands were also tested as Lewis bases. Among these 6 potential promoters, POAP-A gave the best results, and the aldol product were obtained in moderate to good yields up to 80%, and with moderate enantioselectivities (the highest, 66%) after standard optimization studies. Aldehyde screening experiments provided the highest enantioselectivity (68%) with 2- naphthaldehyde.

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Citation Formats
D. Tan, “Silicon tetrachloride mediated asymmetric aldol addition reaction,” M.S. - Master of Science, Middle East Technical University, 2013.