Heterologous biosynthesis of cotylenol and concise synthesis of fusicoccane diterpenoids

• Ye Yuan,
• Zhenhua Guan,
• Xue-Jie Zhang,
• Nanyu Yao,
• Wenling Yuan,
• Yonghui Zhang,
• Ying Ye and
• Zheng Xiang

Beilstein J. Org. Chem. 2025, 21, 1489–1495, doi:10.3762/bjoc.21.111

• .21.111 Abstract A novel strategy for the synthesis of fusicoccane diterpenoids is reported. By harnessing the biosynthetic pathways of brassicicenes and fusicoccins, cotylenol was produced in an engineered Aspergillus oryzae strain. We further achieved the concise synthesis of three fusicoccane

• diterpenoids, including alterbrassicicene E and brassicicenes A and R in 4 or 5 chemical steps from brassicicene I. This strategy lays the foundation for the preparation of fusicoccane diterpenoids and their analogues for biological studies. Keywords: cotylenol; fusicoccane diterpenoids; heterologous

• that cotylenin A and its aglycone, cotylenol (3), induce differentiation in murine and human myeloid leukemia cells [13]. Cotylenin A and fusicoccin A also act synergistically with interferon-α or rapamycin to induce apoptosis in cancer cell lines [14][15][16]. However, cotylenin A cannot be produced

Chemo-enzymatic total synthesis: current approaches toward the integration of chemical and enzymatic transformations

• Ryo Tanifuji and
• Hiroki Oguri

Beilstein J. Org. Chem. 2024, 20, 1693–1712, doi:10.3762/bjoc.20.151

• biosynthetic enzymatic transformations with chemical conversions. This review focuses on the total synthesis of natural products and classifies the enzymatic reactions into three categories. The total synthesis of five natural products: cotylenol, trichodimerol, chalcomoracin, tylactone, and saframycin A, as

• stereoselective cyclization reactions. This review aims to provide an overview of these approaches and parallel comparisons with original biosynthetic pathways by highlighting five examples of chemo-enzymatic total syntheses of natural products reported since 2017. The examples are the synthesis of cotylenol (1

• comprehensive understanding of the chemo-enzymatic synthetic approach, we refer the reader to recent excellent reviews that provide multiple perspectives on the topic [1][2][3][4][5][6][7][8][9][10]. Review Late-stage oxidative transformations of natural product scaffolds: cotylenol and brassicicenes Chemo

Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series

• Cécile Alleman,
• Charlène Gadais,
• Laurent Legentil and
• François-Hugues Porée

Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23

• . Further functionalization steps finally furnished (+)-ophiobolin A (8). In the fusicoccanes family, cotylenol (50), the aglycon of cotylenin A (131) (see section 3.1), is a fungal metabolite which displays various interesting biological activities [28]. For example, it expresses a moderate cytotoxicity

• against human myeloid leukemia cells, and stabilizes the 14-3-3 – TASK3 protein–protein interaction [29][30]. Sugita et al. investigated the synthesis of the core structure of cotylenol (50) first through an RCM approach on the advanced intermediate 47 (Scheme 7) [31]. Despite many attempts, the authors