tailieunhanh - Organocatalysis Episode 4

Tham khảo tài liệu 'organocatalysis episode 4', kỹ thuật - công nghệ, cơ khí - chế tạo máy phục vụ nhu cầu học tập, nghiên cứu và làm việc hiệu quả | 78 D. Enders . Huttl O. Niemeier Fig. 8. Proposed catalytic cycle of the triple cascade NO2 Michael addition Biomimetic Organocatalytic C-C-Bond Formations 79 X CH2 O n 0 1 2 Scheme 17. Asymmetric organocatalytic three-component multistep reaction cascade 80 D. Enders . Huttl O. Niemeier 99 01 dr and we were pleased that in all cases nearly complete enan-tiocontrol 97 to 98 ee was reached. This cascade reaction generates four stereogenic centers and theoretically could give rise to 24 16 different stereoisomers. We note that in fact this asymmetric cascade forms enantioselectively just two diastereomers a-nitro epimers which are easy to separate by flash chromatography. The reason for the high stereoselectivity is the first Michael addition which is known to proceed with high diastereo- and enantiose-lectivity List et al. 2001 Enders and Seki 2002 . Clearly this selectivity is kept or enhanced in the second step via a sterically favorable interaction between the iminium species and the nitroalkane Prieto et al. 2005 . The relative and absolute configurations of the cyclohexene car-baldehydes 72 were determined by 1H-NMR NOE experiments and X-ray crystallography in several cases which are in agreement with respective related organocatalytic conjugate additions. In addition we used this method to develop a one-pot procedure to construct polyfunctionalized tricyclic carbon frameworks which contain up to eight stereogenic centers with high stereocontrol Scheme 18 Enders et al. 2007b . Such functionalized decahydroacenaphthylene n 0 and decahydrophenalene n 1 carbon cores are typical structural features of diterpenoid natural products such as the hainanolides and amphilectanes Piers and Romero 1993 Li et al. 2004 . The assembly of the condensed polycyclic structures 76 and 77 was accomplished by using the organocatalyzed domino Michael Michael aldol condensation sequence Enders and Huttl 2006 starting from the simple aldehyde 73 which already bears a diene .

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