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Volumn , Issue 15, 2008, Pages 2628-2634

Highly stereoselective metal-mediated entry to functionalized tetrahydrothiophenes by Barbier-type carbonyl-addition reactions

Author keywords

Aldehydes; C C coupling; Nucleophilic addition; Sulfur heterocycles; Synthetic methods

Indexed keywords


EID: 53849144301     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200800067     Document Type: Article
Times cited : (8)

References (69)
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    • All of the work in this paper was carried out by using L-proline as the catalyst. However, the use of (S)-2-[bis(3,5-bis(trifluoromethyl) phenyl)(trimethylsilyloxy)methyl]pyrrolidine would lead to an asymmetric synthesis
    • All of the work in this paper was carried out by using L-proline as the catalyst. However, the use of (S)-2-[bis(3,5-bis(trifluoromethyl) phenyl)(trimethylsilyloxy)methyl]pyrrolidine would lead to an asymmetric synthesis.
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    • The lone pairs of electrons of the carbonyl oxygen atom can be considered as hard Lewis base sites. Coordination of these lone pairs to Lewis acids lowers the electron density at the oxygen atom and lowers the energy of the lowest unoccupied molecular orbital, the C=Oπ* orbital, which activates the group towards nucleophilic attack, which thus explains why the bromoallylation addition reaction benefits from the presence of additives. Because the proton is the smallest possible Lewis acid, it may be possible that in the dilute acidic medium provided by the presence of hydrobromic acid in the bromoallylation reaction, protonation of the carbonyl group occurs, which facilitates the addition process by the nucleophile. The role of the hafnium- and bismuth-derived additives may be explained in terms of Lewis acid, which activates both the carbonyl group as well as the softness of the organometallic reagent, probably through transmetallation of the initially formed organometallic re
    • The lone pairs of electrons of the carbonyl oxygen atom can be considered as hard Lewis base sites. Coordination of these lone pairs to Lewis acids lowers the electron density at the oxygen atom and lowers the energy of the lowest unoccupied molecular orbital, the C=Oπ* orbital, which activates the group towards nucleophilic attack, which thus explains why the bromoallylation addition reaction benefits from the presence of additives. Because the proton is the smallest possible Lewis acid, it may be possible that in the dilute acidic medium provided by the presence of hydrobromic acid in the bromoallylation reaction, protonation of the carbonyl group occurs, which facilitates the addition process by the nucleophile. The role of the hafnium- and bismuth-derived additives may be explained in terms of Lewis acid, which activates both the carbonyl group as well as the softness of the organometallic reagent, probably through transmetallation of the initially formed organometallic reagent with hafnium(IV) chloride or bismuth(III) chloride.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.