DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Oh, Dong-Young | - |
dc.contributor.advisor | 오동영 | - |
dc.contributor.author | Gil, Jun-Mo | - |
dc.contributor.author | 길준모 | - |
dc.date.accessioned | 2011-12-13T04:28:57Z | - |
dc.date.available | 2011-12-13T04:28:57Z | - |
dc.date.issued | 2001 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=165832&flag=dissertation | - |
dc.identifier.uri | http://hdl.handle.net/10203/31559 | - |
dc.description | 학위논문(박사) - 한국과학기술원 : 화학과, 2001.2, [ iv, 90 p. ] | - |
dc.description.abstract | The reaction of organocopper (Ⅰ) reagents with 1-alkynylphosphonates affords a rapid entry into a variety of vinylic phosphonates with regio- and stereospecific isomers and high yields in a one-pot process. 1-Alkynyl phosphonates are easily converted into 1-phosphonyl-2,2-dialkyl vinylcopper (Ⅰ) intermediates by treatment with organocopper (Ⅰ) reagents. The intermediates react with a variety of electrophiles to give the vinyl phosphonates derivatives RR``C=$C(E)PO_3Et_2$ (E= H, I, Me, allyl, SePh, TePh, $SiMe_3$). The stereochemistry of the carbocupration of 1-alkynyl phosphonates with organocopper (Ⅰ) reagents is observed to occur with syn-addition (R= H, n-Bu, n-Hex, $CH_2OBn$, Ph) and unexpected anti- addition in the case of R= t-Bu. The β-keto-ω-alkenyl phosphonates affords the mono- and spirocyclic α-phosphonato-α,β-unsaturated cycloenones (β``-ketovinyl phosphonates) via ozonolysis-aldol sequence with the aid of p-TsOH and $Et_3N$ as catalysts. Lithiated alkylphosphonates are allylated with allyl bromide and undergo epoxidation with MCPBA, to give γ,δ-epoxyalkylphosphonates, which are dissolved in THF and treated with n-BuLi at -78℃ to afford the hydroxymethyl-cyclopropylphosphonates via epoxide opening. The 1-formylalkanephosphonates are obtained by the ozonolysis of the corresponding 1-alkylated allylphosphonates, which have been previously prepared by treatment with n-BuLi, followed by addition of alkyl halides. The allylphosphites with MgBrCl without the solvent are rearranged to the allylphosphonates. The allylphosphites undergo a stereoselective and regioselective rearrangement to the allylphosphonates containing Ph, p-ClPh, p-MeOPh, 2-furan, 3-thiophene at 3-position of phosphonates and the configuration of olefin is only E-form. However the rearrangements of allylphosphites containing $p-(Me)_2NPh$, 1-hexene give mixtures. | eng |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.subject | double bond | - |
dc.subject | organic | - |
dc.subject | HIV | - |
dc.subject | phosphorus | - |
dc.subject | vinyl | - |
dc.subject | 바이닐 | - |
dc.subject | 이중결합 | - |
dc.subject | 유기합성 | - |
dc.subject | 에이즈 | - |
dc.subject | 인 | - |
dc.title | (The) study on the synthesis & applications of vinyl or allyl phosphorus derivatives | - |
dc.title.alternative | 바이닐, 알릴 인 유도체의 합성과 응용에 관한 연구 | - |
dc.type | Thesis(Ph.D) | - |
dc.identifier.CNRN | 165832/325007 | - |
dc.description.department | 한국과학기술원 : 화학과, | - |
dc.identifier.uid | 000975023 | - |
dc.contributor.localauthor | Oh, Dong-Young | - |
dc.contributor.localauthor | 오동영 | - |
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