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  • 02월 20일 17시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능

제113회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Theoretical Investigation on the Reaction Mechanism of Gold(I)-Catalyzed Cyclosiomerization of Alkynyl Hydroxyallyl Tosylamides to 4-oxa-6-azatricyclo[,8]octanes

2014년 2월 13일 17시 56분 51초
ORGN.P-803 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
4월 16일 (수요일) 16:00~19:00
저자 및
정대로, 강윤경*
상명대학교 화학과, Korea

Developing a new synthetic method via transition metal-catalyzed reaction is one of the major research areas in organometallic chemistry. Cycloisomerization reactions of N-tethered enyne have been of great interest due to their wide applicability toward the synthesis of variety of cyclized compounds. Recently, Chung and coworkers have reported Au(I)-catalyzed cycloisomerizations of alkynyl hydroxyallyl tosylamides, which gave a totally new 4-oxa-6-azatricyclo[,8] compound. Other metal catalysts that include Rh, Ir, Pd, and even Au metals have only given Alder-ene type products. Here we investigated the reaction mechanism that rationalizes the production of unprecedented 4-oxa-6-azatricyclo[,8] compound by using a density functional theory (DFT) calculation. The reaction starts from the 6-endo-dig cyclization (I), followed by a transannulation between the nitrogen atom and the carbon atom attached to the gold cation (II). Shift of the catalyst moiety leads to a formation of III which may equilibrate with IV. Because of the significant carbocationic character at the alkynyl carbon adjacent to the N-Ts group in IV, a nucleophilic addition of the hydroxyl oxygen occurs to give V. Proton transfer followed by protodemetalation in V affords the product and regenerates the gold(I) catalyst in the catalytic cycle.