多官能基之碳環和雜環分子之創新有機催化反應之發展

Development Of Innovative Organocatalytic Reaction Methods For The Asymmetric Synthesis Of Highly Functionalized Carbocycles And Heterocycles

丹尼丁(Nitin Shivaji Dange)

指導教授 ： 洪伯誠

國立中正大學/理學院/化學暨生物化學系/博士(2012年)

摘要

多官能基之碳環和雜環分子之創新有機催化反應之發展

關鍵字

有機催化

並列摘要

This thesis accumulates our innovation in the field of asymmetric organocatalysis via sequential, cascade and one-pot reaction strategies. Second chapter introduces the first sequential organocatalytic Stetter and Michael-Aldol condensation reaction with certain evidence of kinetic asymmetric transformation. This reaction provides a simple and direct method for the stereoselective and enantioselective construction of fully functionalized cyclopentene derivatives with three contiguous chiral centers. The structures as well as the absolute configurations of adducts 51 were confirmed by X-ray analysis. Third chapter introduces unprecedented organocatalytic sequential Stetter and Michael-Aldol reaction. Synthesis of cyclopentane ring with all five-carbon stereocenters and tertiary alcohol quaternary stereocenter utilizing dynamic kinetic symmetric transformation. The introduction of an intramolecular H-bonding strategy in this system for increasing the yields of Stetter product, enabling DYKAT in Michael-Aldol reaction and obtaining a stable β-hydroxyaldehyde is especially distinguished features of this methodology. The structures as well as the absolute configurations of adducts 58 and 59 were confirmed by X-ray analysis. Forth chapter introduces organocatalytic one-pot Michael-Knoevenagel condensation-hetero-Diels-Alder reaction capable of synthesizing a variety of isochromene pyrimidinedione derivatives 68 bearing five stereocenters with excellent diastereoselectivity and enantioselectivities (up to 99 %). One-pot four consecutive reactions via organocatalysis provide an ecological and economical protocol. Excellent diastereoselectivities in intramolecular hetero-Diels-Alder reaction by a remote stereogenic center generated in situ via organocatalysis is a key feature and excellent strategy of this methodology. X-ray analysis of the appropriate adducts (80a, 80b and 79) confirm the structure and absolute configurations of the isochromene pyrimidinedione derivatives.

並列關鍵字

Organocatalytic

參考文獻

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