2001 Fiscal Year Final Research Report Summary
Studies on the Through Space n_0 → π^* and n_0 → σ^* Interaction
| Project/Area Number |
11672126
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | Kyoto Pharmaceutical University |
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Principal Investigator |
NISHIDE Kiyoharu Kyoto Pharmaceutical University, Associate Professor, 薬学部, 助教授 (10237711)
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| Co-Investigator(Kenkyū-buntansha) |
NODE Manabu Kyoto Pharmaceutical University, Professor, 薬学部, 教授 (60027076)
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| Project Period (FY) |
1999 – 2000
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| Keywords | Fluoro group / Cyano group / X-Ray Crystallographic Analysis / Through Space n_F → π^* Interaction / Stereoselective Protonation / Aliphatic Fluorocyanides / Diels-Alder Reaction / Nucleophile-Electrophile Interaction |
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| Research Abstract |
We have investigated novel through-space n → π^* interactions to provide a new idea for regulation of the conformation of acyclic alkane compounds having fluoro and cyano groups to have the lager dipole moment. The results are summarized as follows : 1) An intramolecular n_F → π^* through-space attractive interaction has been found in 4-fluoro-2- (4-hydroxy- and 4-methoxyphenyl) decanenitriles by means of X-ray crystallographic analyses, 2) The new interaction makes it possible to freeze the conformation of their alkyl chain to have the larger dipole moment, 3) A syn diastereoselective protonation has been demonstrated on 4-fluore-2- (4-methoxyphenyl) decanenitriles due to the new interaction forming a pseudo five-membered ring including F and C (CN), 4) The new intermolecular n_0 → π^* through-space attractive interaction has been suggested to be the major controlling factor of endo/exo stereoselectivity over the usual Alder's second-orbital interaction in a Diels-Alder reaction of allene-1,3-dicarboxylates and N-alkoxycarbonylpyrroles.
We believe that these new findings are significant for the organic chemistry basis.
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