The synthesis and development of new catalyst with the bipyridine scaffold.

1 Abstract Chiral N,N'-dioxides serve as very useful catalysts in various enantioselective reactions. I developed a simple and efficient method for preparation of new unsymmetrically substituted axially chiral bis(tetrahydroisoquinolines)-N,N'-dioxides, based on "one-pot" [2+2+2]-cyclotrimerization of a tetrayne with benzonitrile and (R)-tetrahydrofurancarbonitrile catalyzed by CpCo(CO)2 under microwave irradiation (scheme 1)1,2 . First, the prepared chiral N,N'-dioxides were used as catalysts in highly enantioselective allylations of variously substituted aromatic, aliphatic and α,β-unsaturated aldehydes. The corresponding homoallylalcohols were obtained with ee up to 99%. Two obtained chiral homoallylalcohols prepared by allylation were used as a building-blocks for synthesis of some natural products such as (S)-(-)-Goniothalamin (scheme 2)3 . Second, the chiral N,N'-dioxides were also used for the epoxide ring opening of various meso-epoxides with tetrachlorosilane giving rise to chlorohydrines in moderate enantioselectivities (up to 64% ee) (scheme 3)4 . N N OScheme 1 + N N O O O CpCo(CO)2 MCPBA O NC NC SiCl3 Cat. (1-5mol%) O O (S)-(-)-Goniothalamin, 97% ee Ph R OH up to 99% ee Scheme 2 R R R = phenyl, alkyl O OHClSiCl4 up to 64% ee R H O R= Ar, alkyl, ArCH=CH, alkyl-CH=CH Ph H Scheme 3 Cat. O Cat...