绿色催化化学之子计画.docVIP

補助本校教師出席國際學術會議報告 99年 6 月 27日 報告人姓名 林文偉 服務單位 及職稱 師大化學系 助理教授 會議時間 99/6/22 - 99/6/25 會議地點 中國北京 會議 名稱 第十一屆Tetrahedron Symposuim 發表論 文題目 Pyrrolidine-Type Organocatalysts Bearing Sulfone Moieties in Asymmetric Michael Addition Reactions 報告內容： 一、參加會議經過 六月二十二日下午抵達會場後即為poster section ，也有機會和北京大學席振峰教授及大會秘書長姚祝軍教授進行研究交流和討論。 六月二十三日至六月二十五日間除了參加會議，進行學術交流和討論外，也有機會可以聆聽國際著名學者發表演說其重大的發現。 六月二十六日中午在北京搭機，下午返抵國門。 二、參加會議心得 此會議（Tetrahedron Symposuim）子計畫此外， 三、建議事項 此次會議可以得知國外的研究風氣十分鼎盛，學術能量也十分充足，應多鼓勵校內師長或研究生多加參與。 四、攜回資料 論文集一本 五、論文內容 五、論文內容： Asymmetric organocatalysis of carbon-carbon bond formation is of importance in organic synthesis. Among them, the most successful development of chiral organocatalysts for the asymmetric Michael reaction includes pyrrolidine-type organocatalysts bearing H-bond functions,1 bulky groups,2 salt moieties,3 and phosphine oxide function.4 Recently, we have developed a new type of organocatalyst, (S)-2-((naphthalen-2-ylsulfonyl)methyl)pyrrolidine, prepared in three steps from (S)-N-Boc-2-[((4-toluenesulfonyl)oxy)methyl]pyrrolidine in 62% overall yield. It shows very high catalytic activity toward the direct asymmetric Michael reaction of cyclohexanone and nitroolefins. All the corresponding adducts can be furnished in 90–99% yields and with up to 98% ee and over 99:1 dr on water in the presence of this catalyst (15 mol %) without any additive (Scheme 1).5 Scheme 1. A series of new type of organocatalysts 1a-b and 2a-b bearing a pyrrolidine and a sulfide or sulfone moiety were easily prepared, and the remarkable effects of sulfone moiety and Ar group of catalysts 1 or 2 were shown (Scheme 2 and Table 1). After careful optimization of the reaction condition, the enantioselectivity of 5a can be up to 98% (Table 2). Scheme 2. Table 1. Screening of catalysts 1a, 1b, 2a and 2b for the Michael addition of cyclohexanone (3a) to β-nitrostyrene (4a).a Entry Cat. Time [h] Yield [%]b syn/antic ee [%] synd 1 1a 1.