천연물 총 합성에 대한 다양한 접근방법 연구

Abstract

( E )-β-borylstyrene 을 다이에노파일로 이용하여 3,5-dibromo-2-pyrone 과의 Diels-Alder 고리화 반응을 이용하여 (±)-1- epi -pancratistatin 과 (±)-pancratistatin 의 합성경로를 밝혀내었다. 고리화합물의 보로네이트 그룹은 산화되어 C1 위치의 (±)-1- epi -pancratistatin 과 (±)-pancratistatin 의 OH 그룹을 제공하였다. 아자 마이클 첨가 / 트리플레이팅 접근 방법을 통한 새로운 아미노 인돌의 합성 경로를 개발하였다. 뒤이은 하이드라자이드 커플링과 염화 아연을 이용한 인돌화 반응으로 위치선택적 인돌을 합성하였다. 이 방법을 통하여 (±)-aspidospermidine 의 총 합성 방법을 개발하였으며 (±)-tabersonine 과 (±)- kopsihanianine A 의 새로운 합성 밥법을 제시하였으며 그에 대하여 연구하였다.|New synthetic routes to (±)-1-epi-pancratistatin and (±)-pancratistatin were developed, utilizing (E)-β-borylstyrene as a dienophile for the inverse electron-demand Diels-Alder cycloaddition with 3,5-dibromo-2-pyrone. The boronate in the cycloadduct was readily oxidized to ultimately provide the C1-OH of (±)-1-epi-pancratistatin and (±)-pancratistatin. A new synthetic route to amino indole was developed utilizing base-mediated aza-Michael addition / triflating approach. The aza-Michael addition permitted a facile generation of desired triflate for regioselective indolization. Subsequent hydrazide coupling and zinc chloride mediated indolization gave regioselectivly indoles. With this method I completed formal synthesis of (±)-aspidospermidine. Routes for syntheses of (±)-tabersonine and (±)- kopsihanianine A were proposed and sought.; New synthetic routes to (±)-1-epi-pancratistatin and (±)-pancratistatin were developed, utilizing (E)-β-borylstyrene as a dienophile for the inverse electron-demand Diels-Alder cycloaddition with 3,5-dibromo-2-pyrone. The boronate in the cycloadduct was readily oxidized to ultimately provide the C1-OH of (±)-1-epi-pancratistatin and (±)-pancratistatin. A new synthetic route to amino indole was developed utilizing base-mediated aza-Michael addition / triflating approach. The aza-Michael addition permitted a facile generation of desired triflate for regioselective indolization. Subsequent hydrazide coupling and zinc chloride mediated indolization gave regioselectivly indoles. With this method I completed formal synthesis of (±)-aspidospermidine. Routes for syntheses of (±)-tabersonine and (±)- kopsihanianine A were proposed and sought.