Total Synthesis of the Marine Cyclic Depsipeptide Lagunamide D

Lagunamide D is a structurally distinct 26-membered cytotoxic cyclic depsipeptide, originally isolated from a marine cyanobacterium. It exhibits potent antiproliferative activity in the low nanomolar range against A549 human lung adenocarcinoma cells and HCT116 colon cancer cells. A significant chal...

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Main Authors: Huiru Nan, Xiong-En Long, Jianfei He, Hailiang Xing, Min-Jing Cheng, Jin-Bao Peng, Tao Ye, Jia-Lei Yan, Junyang Liu
Format: Article
Language:English
Published: MDPI AG 2025-02-01
Series:Marine Drugs
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Online Access:https://www.mdpi.com/1660-3397/23/3/99
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author Huiru Nan
Xiong-En Long
Jianfei He
Hailiang Xing
Min-Jing Cheng
Jin-Bao Peng
Tao Ye
Jia-Lei Yan
Junyang Liu
author_facet Huiru Nan
Xiong-En Long
Jianfei He
Hailiang Xing
Min-Jing Cheng
Jin-Bao Peng
Tao Ye
Jia-Lei Yan
Junyang Liu
author_sort Huiru Nan
collection DOAJ
description Lagunamide D is a structurally distinct 26-membered cytotoxic cyclic depsipeptide, originally isolated from a marine cyanobacterium. It exhibits potent antiproliferative activity in the low nanomolar range against A549 human lung adenocarcinoma cells and HCT116 colon cancer cells. A significant challenge associated with lagunamide D is its propensity for intramolecular acyl migration, which leads to the formation of a contracted 24-membered analog, lagunamide D′. This structural rearrangement complicates its isolation, characterization, and synthesis. In this study, the total synthesis of lagunamide D was achieved in a 14-step longest linear sequence, starting from the known intermediate <b>17</b>, with an overall yield of 4.6%. The synthetic strategy involved several key transformations, including Ghosh’s TiCl<sub>4</sub>-promoted anti-aldol reaction, Corey–Bakshi–Shibata reduction (CBS reduction), cross-metathesis, Pinnick oxidation, and Yamaguchi esterification. Furthermore, this synthetic effort unambiguously confirmed the stereochemistry of the natural product.
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publisher MDPI AG
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series Marine Drugs
spelling doaj-art-5cc5be767f5f4237a4a8b3fb3b15e2792025-08-20T02:11:11ZengMDPI AGMarine Drugs1660-33972025-02-012339910.3390/md23030099Total Synthesis of the Marine Cyclic Depsipeptide Lagunamide DHuiru Nan0Xiong-En Long1Jianfei He2Hailiang Xing3Min-Jing Cheng4Jin-Bao Peng5Tao Ye6Jia-Lei Yan7Junyang Liu8School of Pharmacy and Food Engineering, Wuyi University, Jiangmen 529020, ChinaSchool of Pharmacy and Food Engineering, Wuyi University, Jiangmen 529020, ChinaSchool of Pharmacy and Food Engineering, Wuyi University, Jiangmen 529020, ChinaSchool of Pharmacy and Food Engineering, Wuyi University, Jiangmen 529020, ChinaCenter for Bioactive Natural Molecules and Innovative Drugs, and Guangdong Province Key Laboratory of Pharmacodynamic Constituents of TCM and New Drugs Research, College of Pharmacy, Jinan University, Guangzhou 510632, ChinaSchool of Pharmacy and Food Engineering, Wuyi University, Jiangmen 529020, ChinaState Key Laboratory of Chemical Oncogenomics, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, ChinaSchool of Pharmacy and Food Engineering, Wuyi University, Jiangmen 529020, ChinaSchool of Pharmacy and Food Engineering, Wuyi University, Jiangmen 529020, ChinaLagunamide D is a structurally distinct 26-membered cytotoxic cyclic depsipeptide, originally isolated from a marine cyanobacterium. It exhibits potent antiproliferative activity in the low nanomolar range against A549 human lung adenocarcinoma cells and HCT116 colon cancer cells. A significant challenge associated with lagunamide D is its propensity for intramolecular acyl migration, which leads to the formation of a contracted 24-membered analog, lagunamide D′. This structural rearrangement complicates its isolation, characterization, and synthesis. In this study, the total synthesis of lagunamide D was achieved in a 14-step longest linear sequence, starting from the known intermediate <b>17</b>, with an overall yield of 4.6%. The synthetic strategy involved several key transformations, including Ghosh’s TiCl<sub>4</sub>-promoted anti-aldol reaction, Corey–Bakshi–Shibata reduction (CBS reduction), cross-metathesis, Pinnick oxidation, and Yamaguchi esterification. Furthermore, this synthetic effort unambiguously confirmed the stereochemistry of the natural product.https://www.mdpi.com/1660-3397/23/3/99lagunamide Dmarine natural productsdepsipeptidetotal synthesis
spellingShingle Huiru Nan
Xiong-En Long
Jianfei He
Hailiang Xing
Min-Jing Cheng
Jin-Bao Peng
Tao Ye
Jia-Lei Yan
Junyang Liu
Total Synthesis of the Marine Cyclic Depsipeptide Lagunamide D
Marine Drugs
lagunamide D
marine natural products
depsipeptide
total synthesis
title Total Synthesis of the Marine Cyclic Depsipeptide Lagunamide D
title_full Total Synthesis of the Marine Cyclic Depsipeptide Lagunamide D
title_fullStr Total Synthesis of the Marine Cyclic Depsipeptide Lagunamide D
title_full_unstemmed Total Synthesis of the Marine Cyclic Depsipeptide Lagunamide D
title_short Total Synthesis of the Marine Cyclic Depsipeptide Lagunamide D
title_sort total synthesis of the marine cyclic depsipeptide lagunamide d
topic lagunamide D
marine natural products
depsipeptide
total synthesis
url https://www.mdpi.com/1660-3397/23/3/99
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