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https://doi.org/10.1021/ja029276s
DC Field | Value | |
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dc.title | Development of a highly α-regioselective metal-mediated allylation reaction in aqueous media: New mechanistic proposal for the origin of α-homoallylic alcohols | |
dc.contributor.author | Tan, K.-T. | |
dc.contributor.author | Chng, S.-S. | |
dc.contributor.author | Cheng, H.-S. | |
dc.contributor.author | Loh, T.-P. | |
dc.date.accessioned | 2014-10-16T08:25:55Z | |
dc.date.available | 2014-10-16T08:25:55Z | |
dc.date.issued | 2003-03-12 | |
dc.identifier.citation | Tan, K.-T., Chng, S.-S., Cheng, H.-S., Loh, T.-P. (2003-03-12). Development of a highly α-regioselective metal-mediated allylation reaction in aqueous media: New mechanistic proposal for the origin of α-homoallylic alcohols. Journal of the American Chemical Society 125 (10) : 2958-2963. ScholarBank@NUS Repository. https://doi.org/10.1021/ja029276s | |
dc.identifier.issn | 00027863 | |
dc.identifier.uri | http://scholarbank.nus.edu.sg/handle/10635/93575 | |
dc.description.abstract | This paper described a general method to obtain α-adduct homoallylic alcohols using indium, zinc, and tin in water. A new mechanism was proposed to account for the formation of these synthetically difficult-to-obtain molecules. Generally, this method can be performed with a wide range of aldehydes and allylic halides with just 6 equiv of water added, giving the α-adduct in high selectivities. To account for the origin of the α-homoallylic alcohol, the reaction mechanism was carefully studied using 1H NMR, a crossover experiment, and the inversion stereochemical studies of 22β γ-adduct homoallylic sterol to the 22α α-adduct homoallylic sterol. From the results of mechanism studies, it is possible that two mechanism pathways coexisted in the metal-mediated α-regioselective allylation. The metal salts formed from the metal-mediated allylation can catalyze the γ-adduct to undergo a bond cleavage to generate the parent aldehyde in situ followed by a concerted rearrangement, perhaps a retroene reaction followed by a 2-oxonia[3,3]-sigmatropic rearrangement to furnish the α-adduct. The α-adduct can also be synthesized via the formation of an oxonium ion intermediate between the γ-adduct and the unreacted aldehyde. The proposed mechanisms were further supported by experimental findings from the addition of InBr3 to γ-adduct under similar conditions. | |
dc.description.uri | http://libproxy1.nus.edu.sg/login?url=http://dx.doi.org/10.1021/ja029276s | |
dc.source | Scopus | |
dc.type | Article | |
dc.contributor.department | CHEMISTRY | |
dc.description.doi | 10.1021/ja029276s | |
dc.description.sourcetitle | Journal of the American Chemical Society | |
dc.description.volume | 125 | |
dc.description.issue | 10 | |
dc.description.page | 2958-2963 | |
dc.description.coden | JACSA | |
dc.identifier.isiut | 000181409500043 | |
Appears in Collections: | Staff Publications |
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