Research on the Biomimetic Construction of Propeller-Shaped Dual Lactone Ring System in Cephalotanin B

doi:10.6023/cjoc202408028

Abstract

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

Cite this article

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.

Cephalotanin B中螺旋桨型双内酯环系的仿生构建研究