1993 Fiscal Year Final Research Report Summary
Sigmatropic Ring Expansion : Quantitative Evaluation of the Transition States and its Synthetic Application to Natural Products
| Project/Area Number |
04807155
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Chemical pharmacy
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| Research Institution | Osaka University of Pharmaceutical Sciences |
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Principal Investigator |
HARUSAWA Shinya Osaka University of Pharmaceutical Sciences, Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (90167601)
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| Project Period (FY) |
1992 – 1993
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| Keywords | Sigmatropic Rearrangemennt / (Z)-Duoble Bonds / Transition State / MM Computations / Yellow Scale Pheromone / Cyclic Allenes |
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| Research Abstract |
We recently reported that the highly stereoselective synthesis of (Z)-or (E)-double bonds in 10-membered thiolcarbonates was achieved by controlling chairlike-boat-like transition states in the [3,3] sigmatropic rearrangement of 8-membered thionocarbonates. Interestingly, the respective olefin geometry in the staring materials was converted to the opposite geometry with complete isomeric purity.
In order to examine the highly stereoselectivity in these systems, a combination of MM and MO-SCAN compyutations was devised to evaluate the proposed transition states (T_c and T_B).
The synthetic utility of the present methodology was demonstrated by synthesis of the yellow scale pheromone. Further, mediummembered heterocyclic allenes were synthesized.
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