(The) study on the synthesis & applications of vinyl or allyl phosphorus derivatives = 바이닐, 알릴 인 유도체의 합성과 응용에 관한 연구

Cited 0 time in webofscience Cited 0 time in scopus
  • Hit : 266
  • Download : 0
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.
Advisors
Oh, Dong-Young오동영
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
2001
Identifier
165832/325007 / 000975023
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2001.2, [ iv, 90 p. ]

Keywords

double bond; organic; HIV; phosphorus; vinyl; 바이닐; 이중결합; 유기합성; 에이즈; 인

URI
http://hdl.handle.net/10203/31559
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=165832&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
Files in This Item
There are no files associated with this item.

qr_code

  • mendeley

    citeulike


rss_1.0 rss_2.0 atom_1.0