Highly Diastereoselective Synthesis of 5/6-Fused Bicyclic Ring Systems via Radical Cyano Group Migration

被引：0

作者：

Wu, Chenxi ^{[1
,2
]}

Wu, Dan-Yang ^{[1
,2
]}

Wang, Yu-Hao ^{[1
,2
]}

Wang, Pu-Sheng ^{[1
,2
]}

机构：

[1] Univ Sci & Technol China, Hefei Natl Res Ctr Phys Sci Microscale, Hefei 230026, Anhui, Peoples R China

[2] Univ Sci & Technol China, Dept Chem, Hefei 230026, Anhui, Peoples R China

来源：

ORGANIC LETTERS | 2025年 / 27卷 / 10期

基金：

中国国家自然科学基金;

关键词：

INTERMOLECULAR 2+2 PHOTOCYCLOADDITION; PHOTOCHEMICAL-REACTIONS; CYCLIZATION; CATALYSIS; COMBINATION; LIGHT;

D O I：

10.1021/acs.orglett.5c00270

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Here we report a highly diastereoselective cyano group transfer radical cyclization reaction to construct 5/6-fused bicyclic ring systems that bear three contiguous and congested stereogenic elements, with 100% atom economy under catalyst-free and near-ultraviolet light irradiation conditions. Mechanistic investigations and density functional theory calculations suggest that the diastereoselectivity is governed by the conformational distribution of the triplet diradical intermediate and the rate of reverse intersystem crossing (RISC) before radical coupling.

引用

页码：2406 / 2411

页数：6

共 40 条

[1] Asymmetric Total Synthesis of Crotophorbolone: Construction of the 5/7/6-Fused Ring System via an α-Alkoxy Bridgehead Radical Reaction
Urabe, Daisuke
Asaba, Taro
Inoue, Masayuki
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2016, 89 (10) : 1137 - 1144
[2] TERPENOIDS TO TERPENOIDS - ENANTIOSELECTIVE CONSTRUCTION OF 5,6-FUSED, 5,7-FUSED, AND 5,8-FUSED BICYCLIC SYSTEMS - APPLICATION TO THE TOTAL SYNTHESIS OF ISODAUCANE SESQUITERPENES AND DOLASTANE DITERPENES
MEHTA, G
KRISHNAMURTHY, N
KARRA, SR
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (15) : 5765 - 5775
[3] Development of a method for the synthesis of 6-5-6 fused indole ring systems
Karatjas, Andrew G.
Wang, Hua
Herbert, David K.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2013, 246
[4] FREE-RADICAL RING EXPANSION OF FUSED CYCLOBUTANONES - STEREOSPECIFIC CONSTRUCTION OF 5,7-CIS-FUSED, 6,7-CIS-FUSED, 7,7-CIS-FUSED, 8,7-CIS-FUSED, AND 5,8-CIS-FUSED BICYCLIC SYSTEMS
DOWD, P
ZHANG, W
JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (26): : 7163 - 7171
[5] De novo synthesis of 6-6-5 fused systems through electrochemical decarboxylation and radical domino additions
Yuan, Chengcheng
Liu, Guanru
Guan, Wenjing
Hang, Jinlin
Fang, Zheng
Liu, Chengkou
Guo, Kai
GREEN CHEMISTRY, 2024, 26 (19) : 10308 - 10313
[6] Synthesis of medium-sized bicyclic fused ring systems via fragmentation of cycloadducts derived from tandem cyclization-cycloaddition reactions
Lee, Sean A.
Wei, Xia
Fuertes, Michael J.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2009, 237
[7] INTRAMOLECULAR FREE-RADICAL SUBSTITUTION-REACTIONS OF PYRIDINIUM RINGS - EFFICIENT FORMATION OF [5,6]-FUSED AND [6,7]-FUSED RING-SYSTEMS
MURPHY, JA
SHERBURN, MS
TETRAHEDRON LETTERS, 1990, 31 (24) : 3495 - 3496
[8] Amine-induced Michael/Conia-ene cascade cyclization for establishing 6,6-and 5,7-bicyclic fused ring systems
Lee, Chi-Sing
Li, Wei
Liu, Xiaozu
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2010, 239
[9] TRICYCLO[5.3.0.01,6]DECAN-5-ONE AND TRICYCLO[5.4.0.01,6]UNDECAN-5-ONE - SYNTHESIS AND SELECTIVE TRANSFORMATION TO SPIRO AND FUSED BICYCLIC SYSTEMS
RUPPERT, JF
WHITE, JD
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (07) : 1808 - 1813
[10] Chemistry of bicyclic 5-6 systems: Synthesis of oxazolo[3,2-a]pyridines and their salts with a ring-junction nitrogen atom
Monier, Mohamed
El-Mekabaty, Ahmed
Abdel-Latif, Doaa
Elattar, Khaled M.
SYNTHETIC COMMUNICATIONS, 2019, 49 (20) : 2591 - 2629

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