1994 Fiscal Year Final Research Report Summary
Study of Enantioselective Recognition in Inclusion Crystal
| Project/Area Number |
05640654
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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 |
機能・物性・材料
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| Research Institution | Ehime University |
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Principal Investigator |
MIYAMOTO Hisakazu Ehime University, Faculty of Enginerring, assistant, 工学部, 助手 (30229893)
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| Project Period (FY) |
1993 – 1994
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| Keywords | Host / Guest / Inclusion Crystal / Enatioselective Reaction / Solid state reaction / Photoreaction |
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| Research Abstract |
In a inclusion crystal of chiral host molecules and prochiral guest molecules, the latter is arranged in a chiral form, when conditions are appropriate. Freezing of the chirality of the prochiral guest molecule in the inclusion complex by photoreaction in the solid state, gives optically active phtoreaction product. Some succesful examples are reported.
Enantioselective photocyclization of 2- [N-benzyl-N- (2-propenyl) amino] cyclohex-2-enones (1) to 9-benzoyl-9-azatricyclo [5.2.1.0^<1,6>] decan-2-one (2) was acieved efficiently by photoirradiation in a water suspension of an inclusion compound of 1 with the optically active host compound (3) . For example, photoirradiation of powdered 2 : 1 inclusion crystal of 3 with 1 for 17h gave (+) -2 of 99% ee in 64% yield.
The achiral N-isopropyl-N-methylphenylglyoxylamide molecule forms 2 : 1 host-guest complexes with the two kinds of the chiral host molecules derived from tartaric acid. The guest molecules in both the clathrate crystals, I and I
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I,are converted to the chiral beta-lactam on exposure to a Hg lamp. The crystal structures of I and II were determined by X-rays. The guest molecule in each crystal is hydrogen bonded to the two host molecules. The absolute configurations of the chiral products seem to depend on the conformation of the guest molecules in I and II.
A variety of N,N-diisopropylarylglyoxylamides formed chiral crystals in which the originally symmetrical molecules were arranged in achiral form. Photoreaction of the chiral crystals gave optically active beta-lactam derivatives.
Additionaly, optically pure enantiomers of cis-4-methylcyclohex-4-ene-1,2-dicarboxylic anhydrides, cis-4-methyl-cyclohex-4-ene-1,2-dicarboximides and 3-oxabicyclo [4.3.0] non-7-ene-2-ones have been obtained by optical resolution through enantioselective inclusion complexation with optically active host compounds derived from tartaric acid. Kinetic resolution of cyclohex-4-ene-1,2-dicarboximides and cyclohexane-1,2-dicarboximides by way of enantioselective hydrolysis is also reported. Less
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