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sulfur and phosphorus as chiral auxiliaries in asymmetric synthesis of nitrogen-containing compounds (indolizidine alkaloids, pumiliotoxin). [microform]
sulfur and phosphorus as chiral auxiliaries in asymmetric synthesis of nitrogen-containing compounds (indolizidine alkaloids, pumiliotoxin). [microform]
상세정보
- 자료유형
- 마이크로피시
- 청구기호
- 저자명
- 서명/저자
- sulfur and phosphorus as chiral auxiliaries in asymmetric synthesis of nitrogen-containing compounds (indolizidine alkaloids, pumiliotoxin). - [microform]
- 발행사항
- 형태사항
- 273 p. : microfiches ; 11×15 cm.
- 총서명
- UMI Dissertation
- 주기사항
- Source: Dissertation Abstracts International, Volume: 57-11, Section: B, page: 6932.
- 학위논문주기
- thesis (ph.d.)-- - kansas state university, 1996.
- 초록/해제
- 요약Asymmetric synthetic studies of indolizidine alkaloids: pumiliotoxin 251D (42) and polyhydroxylated indolizidines 6-epicastanospermine (112A) and 8-deoxy-7-epicastanospermine (112B) have been conducted using the $\alpha$-sulfinyl ketimine chemistry strategy. Key intermediates: (8aS)-8-methyleneoctahydro-5-indolizidinone (50), (R)-2-methylhexanal (52), and (+)-(1S, 6S, 7S, 8S, 8aS)-1,6,8-tri ((tert-butyldimethyl-silyl)oxy) -1,2,3,5,6,7,8,8a-octahydro-7-hydroxy-5-indolizinone (127) have been synthesized. Asymmetric reactions of N-benzylidene- and N-alkylidenesulfinimines with methylmagnesium bromide, allylmagnesium bromide and diethylaluminum cyanide were explored and an optically active amino acid, (S)-2-methyl-2-amino-4-pentenoic acid (167) was prepared using this strategy.
- 초록/해제
- 요약Asymmetric Michael addition of chiral allylphosphonamide anions to $\alpha,\beta$-unsaturated carbonyl compounds have been studied. Ethyl 2,3-dihydro-4-oxo-(4H)-pyridine-1-carboxylate (219) was used as the Michael acceptor. The reaction proceeded to furnish the adduct (2S, 4R, 5R)-3-isopropyl-4-methyl-5-phenyl-2-$\{$3-$\{2S$- (4-oxo-hexahydro-(N-ethoxycarbonyl)-pyridyl) $\}$-1-propenyl$\}$-1,3,2-oxazaphospholidine-2-one (226) in 64% yield and 98% ee. The optical purity of 226 was established by converting 226 to diacetal 2S- (2-(1R2S)-1,2-dimethyl-ethylenedioxy) -ethyl-4- ((1R,2S)-1,2-dimethyl-ethylenedioxy) -N-ethoxycarbonylpiperidine (228) and comparing $\sp{13}$C NMR's of 228 with that of 2- (2-(1R,2S)-1,2-dimethyl-ethylenedioxy) -ethyl-4- ((1R,2S)-1,2-dimethyl-ethylenedioxy) -N-ethoxycarbonylpiperidine (232), a mixture of two epimers of 228 at C-2 position. The absolute configuration of the newly formed chiral center in the adduct was established by converting the adduct 226 to the known (+)-(S)-2-ethylpiperidine (235).
- 복제주기
- Microfiche : UMI . microfiches;11×15 cm.
- 일반주제명
- 키워드
- 기타저자
- 기본자료저록
- Dissertation Abstracts International. 57-11B.
MARC
008970923s1996 us eng■001MOKWON00234504
■001AAV9714479
■00519991002114544
■008970923s1996 us eng
■035 ▼a(UnM)AAV9714479
■040 ▼aUnM▼cUnM▼dMOKWON
■090 ▼a540▼bC518s
■1001 ▼achen, jinshan.
■24510▼asulfur and phosphorus as chiral auxiliaries in asymmetric synthesis of nitrogen-containing compounds (indolizidine alkaloids, pumiliotoxin).▼h[microform]
■260 ▼aU.S.▼bkansas state university▼c1996.
■300 ▼a273 p.▼bmicrofiches▼c11×15 cm.
■350 ▼a$50.6
■44000▼aUMI Dissertation
■500 ▼aSource: Dissertation Abstracts International, Volume: 57-11, Section: B, page: 6932.
■502 ▼athesis (ph.d.)--▼bkansas state university▼d1996.
■520 ▼aAsymmetric synthetic studies of indolizidine alkaloids: pumiliotoxin 251D (42) and polyhydroxylated indolizidines 6-epicastanospermine (112A) and 8-deoxy-7-epicastanospermine (112B) have been conducted using the $\alpha$-sulfinyl ketimine chemistry strategy. Key intermediates: (8aS)-8-methyleneoctahydro-5-indolizidinone (50), (R)-2-methylhexanal (52), and (+)-(1S, 6S, 7S, 8S, 8aS)-1,6,8-tri ((tert-butyldimethyl-silyl)oxy) -1,2,3,5,6,7,8,8a-octahydro-7-hydroxy-5-indolizinone (127) have been synthesized. Asymmetric reactions of N-benzylidene- and N-alkylidenesulfinimines with methylmagnesium bromide, allylmagnesium bromide and diethylaluminum cyanide were explored and an optically active amino acid, (S)-2-methyl-2-amino-4-pentenoic acid (167) was prepared using this strategy.
■520 ▼aAsymmetric Michael addition of chiral allylphosphonamide anions to $\alpha,\beta$-unsaturated carbonyl compounds have been studied. Ethyl 2,3-dihydro-4-oxo-(4H)-pyridine-1-carboxylate (219) was used as the Michael acceptor. The reaction proceeded to furnish the adduct (2S, 4R, 5R)-3-isopropyl-4-methyl-5-phenyl-2-$\{$3-$\{2S$- (4-oxo-hexahydro-(N-ethoxycarbonyl)-pyridyl) $\}$-1-propenyl$\}$-1,3,2-oxazaphospholidine-2-one (226) in 64% yield and 98% ee. The optical purity of 226 was established by converting 226 to diacetal 2S- (2-(1R2S)-1,2-dimethyl-ethylenedioxy) -ethyl-4- ((1R,2S)-1,2-dimethyl-ethylenedioxy) -N-ethoxycarbonylpiperidine (228) and comparing $\sp{13}$C NMR's of 228 with that of 2- (2-(1R,2S)-1,2-dimethyl-ethylenedioxy) -ethyl-4- ((1R,2S)-1,2-dimethyl-ethylenedioxy) -N-ethoxycarbonylpiperidine (232), a mixture of two epimers of 228 at C-2 position. The absolute configuration of the newly formed chiral center in the adduct was established by converting the adduct 226 to the known (+)-(S)-2-ethylpiperidine (235).
■533 ▼aMicrofiche▼cUMI▼emicrofiches;11×15 cm.
■590 ▼aSchool code: 0100.
■650 4▼aChemistry, Organic
■653 ▼asulfur▼aand▼aphosphorus▼aas▼achiral▼aauxiliaries▼ain▼aasymmetric▼asynthesis▼aof▼anitrogen-containing▼acompounds▼a(indolizidine▼aalkaloids▼apumiliotoxin).
■690 ▼a0490
■71020▼akansas state university.
■7730 ▼tDissertation Abstracts International▼g57-11B.
■790 ▼a0100
■791 ▼aPH.D.
■792 ▼a1996
