Citation: Yu Kuan, Gao Beiling, Ding Hanfeng. Asymmetric Total Synthesis and Absolute Configuration Reassignment of Indole Alkaloid (+)-Alsmaphorazine D[J]. Acta Chimica Sinica, ;2016, 74(5): 410-414. doi: 10.6023/A16020102 shu

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

Yu Kuan ^† ,
Gao Beiling ^† ,
Ding Hanfeng ^*,,

1.
Department of Chemistry, Zhejiang University, Hangzhou 310028

Corresponding author: Ding Hanfeng, hfding@zju.edu.cn
Received Date: 25 February 2016

Fund Project: the Zhejiang Natural Science Fund for Distinguished Young Scholars LR16B020001the National Natural Science Foundation of China 21472167

Figures(6)

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.].
- alkaloid,
- total synthesis,
- tetracyclic system,
- oxidative cyclization,
- radical reaction
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