铑（Ⅱ）催化α重氮羰基化合物的多组分反应研究-有机化学专业论文.docx

Studies Studies on Rhodium(1I)-catalyzed Multicomponent Reactions of a—Diazocarbonyl Compounds Chong—Dao Lu(Organic Chemistry) Directed by Prof．Ai·-Qiao Mi and Profi Wen·-Hao Hu ABSTRACT Multi—component reactions closely approach the concept of ideal synthesis due to its inherent merits were concerned．HoweveL the use of multi—component reaction in diazo chemistry is limited by the high reactivity of diazo carbenes．Up tO now the research in this field had been just mainly focusing on the 1,3一dipolar cycloaddition reaction of carbonyl ylide．Both chance and challenge exist while applying the concept of multi—component reaction in the diverse diazo chemistry world．Our efforts in this challenging area are well described in this thesis． The thesis explores the first example of chemospecific dioxolane formation from ‘。cross”1，3-dipolar cycloaddition of methyl phenyldiazoacetate with all electron-rich and an electron-deficient atdehyde in the presence of dirhodium acetate catalyst． Carbonyl ylide generated from the carbenoid with the electron-rich aidehyde selectively reacts wi廿l the electron—deficient aldehyde to give 2,4，5-triaryl一 1，3-dioxolanes in hi曲 yields、vith excellent chemoselectivity and diastereoselectivity(C一2／C-4、．Concept of intermolecular trapping of carbonyl yilde was then applied for the efficient synthesis of tRNA synthetase inhibitor analogues． Thus，the three—component 1,3一dipolar cycloaddition reactions of carbonyl ylides derived from diazoindan一1．3-dione and aldehydes、埔th maleimides gave ring fused tetrahydrofurans having three stereocenters in good yield．This is a better route in contrast to the reported three-step approach(condensation，epoxidation and thermal 1．3-dipolar 1．3-dipolar cycloadditio小．At the salne time it was found that aryl aldehydes with orthro—only substituent always gave high diastereoselectivity(C·3(4)／c一5)in the tetrahydrofuran ring ofthe products． in addition，Rh(II)-catalyzed three—component reaction of aryl diazoacetates， alcohol