Convergent Total Synthesis of Kalmanol DOI Open Access
Rong Zhao, Xiaolong Zhao, Ming Yang

и другие.

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 27, 2024

Abstract Kalmanol ( 1 ) is the first isolated kalmane‐type grayanoid featuring a highly oxidized 5/8/5/5 tetracyclic carbon skeleton and 9 contiguous stereocenters. We have accomplished efficient asymmetric total synthesis of in 16 steps from known compounds (20 commercially available starting materials) by modular synthetic strategy. A intermediate was prepared convergent manner through Grignard reaction subsequent ring‐closing metathesis two enantiomerically enriched fragments. The polyhydroxy groups were introduced late‐stage stereo‐ regioselective oxidations.

Язык: Английский

Total Synthesis of Principinol B DOI
Qiang Du,

Zhibo Fan,

Ming Yang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(17)

Опубликована: Фев. 23, 2024

We have accomplished the first and asymmetric total synthesis of principinol B, a grayanoid possessing an oxabicyclo[3.2.1] architecture. A functionalized 5/7/6/5 tetracyclic intermediate was assembled in convergent manner by diastereoselective intermolecular aldol reaction subsequent carbonyl-olefin metathesis two enantiomerically enriched fragments. The architecture containing 6,10-ether bridge constructed Williamson ether synthesis.

Язык: Английский

Процитировано

10

Recent advancements in the chemistry of Diels–Alder reaction for total synthesis of natural products: a comprehensive review (2020–2023) DOI Creative Commons
A. C. Rana, Anupam Mishra, Satish Kumar Awasthi

и другие.

RSC Advances, Год журнала: 2025, Номер 15(6), С. 4496 - 4525

Опубликована: Янв. 1, 2025

This review covers recent advancements in Diels–Alder reaction chemistry for total synthesis of Natural Products (2020–2023) and, where relevant, discusses key structural features and biological activity bioactive natural products.

Язык: Английский

Процитировано

2

Forging the Tetracyclic Core Framework of Rhodomolleins XIV and XLII: A Ring-Distortion Approach DOI

Zhen‐Ning Yang,

Huijuanzi Rao,

Yuhao Yin

и другие.

Organic Letters, Год журнала: 2024, Номер 26(17), С. 3524 - 3529

Опубликована: Апрель 24, 2024

A ring distortion approach for the synthesis of an advanced intermediate en route to rhodomolleins XIV and XLII was described, which led successful construction 5/8/5/5 tetracyclic core framework kalmane diterpenoids. Key steps strategy include oxidative dearomatization-induced (ODI)-Diels-Alder cycloaddition, a Dowd-Beckwith rearrangement, bioinspired Wagner-Meerwein rearrangement.

Язык: Английский

Процитировано

7

Bioinspired Total Synthesis of Natural Products DOI
Lijun Chen, Peng Chen, Yanxing Jia

и другие.

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 27, 2024

ConspectusCurrently, the frontier challenges in total synthesis pertain to increasing synthetic efficiency and enabling divergent of a number natural products. Bioinspired has been well recognized as an effective approach efficiency. Especially, when bioinspired was applied at late-stage skeletal diversification generate various products with distinct carbon skeletons, it held special promise for achieving both goals. In our laboratory, served one two long-standing principles facilitating efficient this Account, we summarize endeavors journeys We categorize work into three parts based on imitation biosynthetic reactions processes.(1) To mimic key cyclization steps. Inspired by process that formed core skeleton, developed new methods enable rapid construction skeletons targeted molecules, ultimately leading their concise synthesis, example, seven-step lamellarins D H featuring oxidative coupling reactions, clavicipitic acid highlighted C-H activation/aminocyclization cascade reaction, eight-step phalarine via coupling, α-cyclopiazonic acid, ten-step speradine C through reaction initiated benzylic carbocation indole. (2) revised pathway proposed us. some cases, processes may be flawed, they contradict basic chemistry. Thus, alternative must investigated. showcase euphorikanin A benzilic acid-type rearrangement bipolarolides B Prins reaction/ether formation cyclization. (3) process. Nature usually synthesizes multitude from common intermediate manner. Biogenic also drawn attention. Compared single-target-oriented skeletal-diversity-oriented remains underexplored due its high challenges. showcased syntheses ten

Язык: Английский

Процитировано

6

Total Synthesis of (+)‐Kalmanol DOI

Tianhao Ma,

Yiming Ma,

Bo Li

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июль 31, 2024

Kalmanol, the flagship member of kalmane diterpene family, possesses a complex and highly oxidized 5/5/8/5 tetracyclic skeleton with nine contiguous stereocenters exhibits significant analgesic effects cardiotoxic properties. We have achieved efficient total synthesis (+)-kalmanol in 22 steps 2.3 % yield. The featured Rh-catalyzed [5+2+1] cycloaddition reaction to construct 5/5/8 tricyclic skeleton, meticulously designed sequence stereoselective oxidations skeleton.

Язык: Английский

Процитировано

4

Review on Catalytic Meinwald Rearrangement of Epoxides DOI Open Access
Yulong Zhang, Bowen Hu, Yushuang Chen

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(59)

Опубликована: Авг. 14, 2024

The past few decades have witnessed tremendous development within epoxides. Among the many known reactions involving epoxide, Meinwald rearrangements represent one of most important and attractive approaches, which can transform epoxides into versatile carbonyl compounds. Given high efficiency this protocol, substantial efforts been made by researchers utilizing multiple catalyst systems. This review provides an overview recent advances in rearrangement (from 2014 onward), along with detailed discussions on mechanistic insights. aims to highlight importance value these methodologies, thereby promoting further investigation application.

Язык: Английский

Процитировано

4

Copper-catalyzed asymmetric cascade diyne cyclization/Meinwald rearrangement DOI

Ji‐Jia Zhou,

Li‐Gao Liu, Zhentao Zhang

и другие.

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 110870 - 110870

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0

Total Syntheses of Highly Oxidized Natural Products DOI Open Access
Yan Wang, Xiangbing Qi

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

Comprehensive Summary Natural products with high oxidation states and complex chemical skeletons exhibit diverse bioactivities due to their unique interactions biological targets. The state is characterized by the presence of multiple oxygen‐containing functional groups such as hydroxyl groups, carbonyl epoxides that are usually tough construct selectively. In recent years, thanks development efficient strategies sophisticated methodologies, significant advancements have been made in total syntheses highly oxidized natural (HONPs). this review, we highlight examples HONPs focusing on tetrodotoxin (TTX) its derivatives, steroidal alkaloids, sesquiterpenes, diterpenoids since 2019. Key Scientists 2005, Yang group applied thioureas ligands Pauson−Khand reaction for synthesis triterpene products. methodological advances achieved a series topologically structural features following years. 2009, Baran established pioneering “two‐phase” approach terpenes, an innovative strategy has inspired numerous field. 2011, Xu Theodorakis (−)‐jiadifenolide, sesquiterpene from Illicium . 2012, Li 6π electrocyclization containing aromatic rings. 2014, Inoue introduced α‐alkoxy bridgehead radical, facilitating unified ryanodane diterpenoids. subsequent radical‐based convergent were employed assembling HONPs. developed type ΙΙ [5+2] reaction, which can be efficiently featuring bridged ring systems. Reisman presented pattern analysis guided synthetic designs complex, isoryanodane diterpenes. 2017, Gao reported photoenolization/Diels‐Alder (PEDA) constructing related polycyclic rings elevated states. 2018, Ding unprecedented oxidative dearomatization‐induced (ODI) cycloaddition/pinacol‐ 1,2‐acyl migration cascade assemble oxygenated bicyclo[3.2.1]octane system, was subsequently grayanane same year, Gui explored “bioinspired” strategic transformations enabled rapid construction core framework steroid terpenoid 2020, Luo successfully synthesized several HONPs, including (−)‐batrachotoxinin, (−)‐zygadenine, diterpenoids, employing elegant strategies. 2021, Zhang site‐specific photochemical desaturation late‐stage skeletal reorganization strategies, enabling divergent sesquiterpenes. 2022, Jia first (−)‐principinol C, accomplished six More recently, Trauner concise tetrodotoxin, particularly strategy.

Язык: Английский

Процитировано

0

Convergent Total Synthesis of (−)-Calidoustene DOI

Weidong Yao,

Ziqi Liu, Hao Ling

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(19), С. 15963 - 15969

Опубликована: Апрель 29, 2025

The first total synthesis of the sesterterpenoid (-)-calidoustene has been accomplished, featuring a stereoselective Michael/aldol cascade to construct trans-hydrindane backbone, tandem Pummerer/Sakurai cyclization establish bicyclo[3.2.1]octane framework, metallaphotoredox enone coupling followed by MHAT-initiated forge congested central C-ring, and late-stage functionalization via Cu-catalyzed desaturation diimide reduction.

Язык: Английский

Процитировано

0

Five decades of endeavor towards total syntheses of grayanane diterpenoids DOI
Qi‐Dong Xia, Hanfeng Ding

Tetrahedron Letters, Год журнала: 2024, Номер 145, С. 155160 - 155160

Опубликована: Июнь 24, 2024

Язык: Английский

Процитировано

2