Asymmetric Total Synthesis and Absolute Configuration Reassignment of Indole Alkaloid (+)-Alsmaphorazine D

doi:10.6023/A16020102

Acta Chim. Sinica ›› 2016, Vol. 74 ›› Issue (5): 410-414.DOI: 10.6023/A16020102 Previous Articles Next Articles

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吲哚生物碱(+)-Alsmaphorazine D的不对称全合成及其绝对构型更正

余宽, 高北岭, 丁寒锋

浙江大学化学系杭州 310028

投稿日期:2016-02-25 发布日期:2016-04-08
通讯作者: 丁寒锋 E-mail:hfding@zju.edu.cn
基金资助:
项目受国家自然科学基金(No. 21472167)及浙江省杰出青年基金(No. LR16B020001)资助.

Asymmetric Total Synthesis and Absolute Configuration Reassignment of Indole Alkaloid (+)-Alsmaphorazine D

Yu Kuan, Gao Beiling, Ding Hanfeng

Department of Chemistry, Zhejiang University, Hangzhou 310028

Received:2016-02-25 Published:2016-04-08
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21472167) and the Zhejiang Natural Science Fund for Distinguished Young Scholars (No. LR16B020001).

1. Asymmetric Total Synthesis and Absolute Configuration Reassignment of Indole Alkaloid (+)-Alsmaphorazine D.PDF(3801KB)

Abstract

The first asymmetric total synthesis of (+)-alsmaphorazine D has been achieved through a traceless chirality transfer strategy, which also enabled absolute configuration reassignment of the natural product. Key steps of this efficient approach entail a catalytic oxidative cyclization [To a solution of indoline ester 8 (5.82 g, 10 mmol) in AcOH (100 mL) were added CAN (550 mg, 1 mmol) and NaOAc (1.64 g, 20 mmol). The reaction vessel was exposed to air through a CaCl₂ tube. The resulting mixture was stirred at 110 ℃ for 12 h before it was concentrated in vacuo. The residue was diluted with H₂O, neutralized with NaHCO₃ (sat. aq.) and extracted with EtOAc. The combined organic layers were washed with brine, dried (Na₂SO₄) and concentrated in vacuo. Flash column chromatography (silica gel, hexanes/EtOAc, V:V=4:1) afforded δ-lactamindole 7 (4.34 g, 75%) as a white amorphous solid], a diastereoselective oxidative cyclic aminal formation [To a stirred solution of mono-ester 13 (5.20 g, 10 mmol, dr=1:1) in acetone (100 mL) at 0 ℃ was added NaHCO₃ (100 mL, sat. aq.). The resulting mixture was stirred for 0.5 h before it was added oxone (12.28 g, 20 mmol) slowly. The reaction mixture was stirred at 0 ℃ for an additional 2 h before it was diluted with H₂O. The aqueous layer was extracted with CH₂Cl₂. The combined organic layers were washed with brine, dried (Na₂SO₄) and concentrated in vacuo. Flash column chromatography (silica gel, hexanes/EtOAc, V:V=3:1) afforded pyrroloindole 6' (1.61 g, 71%) as a white amorphous solid] and an intramolecular radical cyclization [To a stirred solution of ent-5 (250 mg, 0.47 mmol) in benzene (5 mL) at 80 ℃ were added n-Bu₃SnH (152 μL, 0.56 mmol) and AIBN (5 μL, 0.047 mmol). The resulting mixture was stirred for 0.5 h before it was concentrated in vacuo. Flash column chromatography (silica gel, hexanes/EtOAc, V:V=１:1) afforded C(16)-epi-ent-4 (213 mg, 72%) as a colorless oil.].

Key words: alkaloid, total synthesis, tetracyclic system, oxidative cyclization, radical reaction

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Yu Kuan, Gao Beiling, Ding Hanfeng. Asymmetric Total Synthesis and Absolute Configuration Reassignment of Indole Alkaloid (+)-Alsmaphorazine D[J]. Acta Chim. Sinica, 2016, 74(5): 410-414.

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吲哚生物碱(+)-Alsmaphorazine D的不对称全合成及其绝对构型更正

Asymmetric Total Synthesis and Absolute Configuration Reassignment of Indole Alkaloid (+)-Alsmaphorazine D

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