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樟腦磺醯胺衍生之胺化合物與(2S,4R)-4-三異丙基矽氧基-L-脯胺酸之縮合物催化α-矽氧基乙醛與亞胺衍生物進行不對稱Mannich 反應之研究
Thesis

樟腦磺醯胺衍生之胺化合物與(2S,4R)-4-三異丙基矽氧基-L-脯胺酸之縮合物催化α-矽氧基乙醛與亞胺衍生物進行不對稱Mannich 反應之研究

吳欣宴
Masters, 國立清華大學, 化學系
2015

Abstract

太平洋紫杉醇 不對稱合成 Paclitaxel Asymmetric Mannich Reactions
This thesis deals with the use of organocatalyst 75b, comprising of trans-4-TIPSO-L-proline and N-phenyl camphorsulfonamide skeletons, in the asymmetric Mannich reaction of α-silyloxyethanal to N-tosylimines, affording syn 1,2-amino alcohols with reasonable to good chemical yield (31% to 91%), slight to moderate diastereoselectivities (52:48 to 85:15) and moderate to good enatioselectivities (89 to >99% ee of the trans 89 products). An extensive and through screening on the solvents, additives and aldehyde equivalents identified that 5 mol % of the catalyst and 6 mol % of acid additive were able to efficiently provide 87% yield of the addition product with 97 % ee for the 4-methyl substituted example. Furthermore, it was found that the binary IPA-DCM solvent system was important for achieving good yields.

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