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제114회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Theoretical Investigation on the Pt-Catalyzed Cycloisomerization of 1,6-Enynes to Alder-ene type of products

등록일
2014년 8월 28일 15시 41분 05초
접수번호
1117
발표코드
ORGN.P-854 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
10월 15일 (수요일) 16:00~19:00
발표형식
포스터
발표분야
유기화학
저자 및
공동저자
박지은, 강윤경*
상명대학교 화학과, Korea

Transition metal-catalyzed cycloisomerizations of enynes have been of great interest in the field of organic and organometallic chemistry as well as catalysis research. Extensive studies have provided a wide range of chemical transformations that are synthetically useful and atom economical. While Pd- and Au-catalyzed reaction of 1,6-enynes give rise to the formations of variety of products illustrated in the scheme, Pt-catalyzed one provided mainly a bicycle[4.1.0]heptenes (I) for the heteroatom-tethered substrates and single or double exo-cleavage products (V and VI) for the carbon-tethered ones. Diversity of mechanistic proposals have been suggested and part of them were underpinned by the computational analyses, the detailed background of these peculiar results have not been completely elucidated. Here, we have complete the reaction map of the PtCl2-catalyzed cycloisomerization of 1,6-enyne that shows the relative energetics of virtually all possible reaction pathways by using density functional theory (DFT). We have found that the difference in reactivity of N- and C-tethered 1,6-enyne catalyzed by PtCl2 catalyst stems mainly from the large destabilizations of the 6-endo-cyclization product, bicyclo[4.1.0]heptene (I), and transition state that connect these two state of C-tethered 1,6-enyne, which cause the shift of the reaction pathway toward single or double exo-cleavage products (V and VI).


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