Free radical-mediated acylation approach using acylphosphonate derivatives = 아실포스포네이트 화합물을 이용한 라디칼 아실화 반응에 관한 연구

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We have investigated an intriguing possibility of β-elimination of a phosphonate group from an alkoxyl radical. When a-alkoxyl phosphonate was reacted with V-40 as initiator in chlorobenzene for 3 h, aldehyde was isolated in high yield, indicating the facile β-elimination of organophosphorous group from the alkoxyl radical for the first time. On the basis of our findings, we have studied the feasibility of the use of an acylphosphonate as a carbonyl group radical acceptor. Radical cyclization of acylphosphonate in the presence of hexamethylditin at 300 nm for 2 h in benzene gave cyclopentanone in good yield without the formation of the direct reduction product. The reaction can be carried out in the presence of a catalytic amount of hexamethylditin (0.2 equiv) under the similar conditions because initially generated phosphonate radical reacts with an alkyl iodide to generate an alkyl radical. To achieve acylphosphorylation of intramolecular olefinic moiety, photochemical irradiation of ω-alkenoylphosphine oxide is studied along with the acylphosphorylation under thermal condition using benzoylperoxide and diethylphosphite. The cyclizations of phosphonoformates do not occur under thermal and photochemical conditions, apparently due to unfavorable E-conformation in carboxylic esters. However, an alkyl phosphonothiolformate group can act as an alkylthiocarbonyl group equivalent radical acceptor, providing a ready access to a thiolactone synthesis. As an extension of intramolecular approach, intermolecular acylation was studied. However, due to slow rate in intermolecular radical addition to acylphosphonates, the satisfactory yields were not obtained. We designed various cyanophosphonate derivatives for intermolecular radical cyanation. Intermolecular cyanation was successfully achieved under photochemical condition using diethylcyanophosphonate as a radical acceptor.
Advisors
Kim, Sung-Gakresearcher김성각researcher
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
2006
Identifier
254199/325007  / 020025293
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2006.2, [ iii, 135 p. ]

Keywords

Radical ß-elimination acylation cyclization; 라디칼 ß-제거반응 아실화반응 고리화반응

URI
http://hdl.handle.net/10203/31670
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=254199&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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