Cephalotanin B中螺旋桨型双内酯环系的仿生构建研究

doi:10.6023/cjoc202408028

摘要/Abstract

作为三尖杉二萜家族的一员, cephalotanin B复杂的分子结构拥有一个颇为独特的螺旋桨型双内酯环系. 基于已知生物合成路径的推测, 先后探索了两种仿生构建方案, 开发出了一种新颖的环氧开环/消除/双内酯化串联过程, 最终为cephalotanin B独特的螺旋桨型双内酯环系成功发展出一种简单高效的仿生构建策略.

关键词: 天然产物, 复杂结构, 仿生合成

As a member of the family of Cephalotaxus diterpenoids, cephalotanin B possesses a quite unique propeller-shaped dual lactone ring system. Based on known proposal of biosynthetic pathway, two biomimetic construction approaches were explored successively, a novel epoxide-opening/elimination/dual lactonization cascade was exploited, and a brief and efficient biomimetic construction strategy for the unique propeller-shaped dual lactone ring system was developed successfully in the end.

Key words: natural product, complex structure, biomimetic synthesis

引用此文

孙泽众, 金双, 王云侠, 胡向东. Cephalotanin B中螺旋桨型双内酯环系的仿生构建研究[J]. 有机化学, 2025, 45(3): 996-1002.

Zezhong Sun, Shuang Jin, Yunxia Wang, Xiangdong Hu. Research on the Biomimetic Construction of Propeller-Shaped Dual Lactone Ring System in Cephalotanin B[J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 996-1002.

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Entry	R	Base	Solvent	Yield^c/%
1	TMS	LDA	THF	—
2	TMS	LDA	PhMe	—
3	TMS	LiHMDS	PhMe	—
4	TMS	LiTMP	PhMe	—
5	t-Bu	LDA	THF	20 [8b, dr=1∶1 at C(12)]
6	t-Bu	LDA	PhMe	73 [8b, dr=1.4∶1 at C(12)]

Entry	R	Base	Solvent	Yield^c/%
1	TMS	LDA	THF	—
2	TMS	LDA	PhMe	—
3	TMS	LiHMDS	PhMe	—
4	TMS	LiTMP	PhMe	—
5	t-Bu	LDA	THF	20 [8b, dr=1∶1 at C(12)]
6	t-Bu	LDA	PhMe	73 [8b, dr=1.4∶1 at C(12)]

Entry^a	Conditions	Result
1	1 mol/L HCl, THF	NR
2	1 mol/L H₂SO₄, THF	NR
3	48% HBr, THF	NR
4	40% HBF₄, THF	NR
5	HCO₂H, DCM	NR
6	TFA, DCM	ND
7	AcOH, DCM	NR
8	TfOH, DCM	Dec.
9	Cu(OTf)₂, DCM	NR
10	Sc(OTf)₃, DCM	NR
11	BF₃•Et₂O, DCM	Dec.
12	TiCl₄, DCM	Dec.

Entry^a	Conditions	Result
1	1 mol/L HCl, THF	NR
2	1 mol/L H₂SO₄, THF	NR
3	48% HBr, THF	NR
4	40% HBF₄, THF	NR
5	HCO₂H, DCM	NR
6	TFA, DCM	ND
7	AcOH, DCM	NR
8	TfOH, DCM	Dec.
9	Cu(OTf)₂, DCM	NR
10	Sc(OTf)₃, DCM	NR
11	BF₃•Et₂O, DCM	Dec.
12	TiCl₄, DCM	Dec.

Entry	Conditions	Result
1	m-CPBA, NaHCO₃, DCM	NR
2	UHP, TFAA, DCM	NR
3	Acetone, oxone, NaHCO₃, MeCN/H₂O	NR
4	TFK, oxone, NaHCO₃, MeCN/H₂O	NR
5	TBHP, DBU, THF	NR
6	TBHP, Triton B, THF	NR
7	5% NaClO, THF	NR
8	5% NaClO, PTC, THF	NR
9	30% H₂O₂, NaOH, MeOH/H₂O	Dec.
10	30% H₂O₂, Na₂CO₃, MeOH/H₂O	Dec.
11	30% H₂O₂, K₂CO₃, MeOH/H₂O	Dec.
12	30% H₂O₂, NaHCO₃, MeOH/H₂O	Dec.
13	30% H₂O₂, NaH₂PO₄, MeOH/H₂O	15 (trace)
14	30% H₂O₂, t-BuNH₂, MeOH/H₂O	Dec.