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학위논문 동서

(4R)-,(4S)-[4-²H₁]Gerany1 Pyrophosphate(GPP)의 합성에 관한 연구

이도훈

부산: 동아대학교 1997. -

i,42장: 삽도; 26cm. -

학위논문(석사)- 동아대학교 대학원 화학과 전공 1997년8월

영문초록 : In this paper, to evaluate the stereospecificity of the elimination reaction at C3 of the pinyl intermediate (C4 of geranyl precursor) using (4R)- and (4S)-[4-(2)^H_(1)]GPPs as substrates by the pinene cyclases, we report studies on the synthesis of (4R)- and (4S)-[4-(2)^H_(1)]GPPs. We designed process of total synthesis of (4R) and (4S) GPPs according to six reaction steps. The alkylation of the allylic thio ester 21 produced both α-and γ-alkylated products 22(ratio∼4.5:1) and the γ-alkylated products were a mixture of trans- and cis- isomers (ratio∼4:1) Oxidation (m-CPBA, CH_(2)Cl_(2), -25℃)of the partially purified 22 and subsequent rearrangement of the resulting sulfoxide (Et_(2)NH/MeOH, room temperature) gave allylic alcohol 23 Epoxidation was carried out according to the catalytic sharpless epoxidation procedure as described by Tanis et al. Yield of (2S,3S)-(-)-2,3-Epoxy-2,6-dimethyl-5-hepten-l-ol 24 is 3.03 g(91%). Deuterated diols (-)- and (+)-26-d_(1) were prepared by reduction of (-)- and (+)-24 with LiAlD_(4). 0xidation of (-)-26-d_(1) was performed according to the general procedure of Swern oxidation method. The product was used for wittig reaction without further purification. Yield of (-)-28,d_(1) is 264 mg (43%). 29-d_(1) was abtained by oxidation (PCC) and reduction(LiAlH_(4)). The Oxidation (PCC) of (-)-28-d_(1) produced a crude mixture of (E)-and (Z)-aldehydes (i.e., geranial and neral). Pyrophosphorylation of (4R)- and (4S)-29-d_(1) to (4R)- and (4S)-1-d_(1) was performed according to a literature procedure.

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