Recent advances in radical cascade cyclization of 1,n-enynes with trifluoromethylating agents

Shi, Zhuangzhi; Yu, Tongyan; Ma, Hongsheng; Chi, Longxiao; You, Siliang; Deng, Cunbao

doi:10.1016/j.tet.2022.133216

Cited by 3 publications

(1 citation statement)

References 82 publications

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“…Despite the recent enormous development of radical asymmetric catalysis [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] , investigations of chemocatalytic enantioselective atom transfer reactions have only met with limited success using chiral Lewis acid catalysis 21,22 , organocatalysis 23,24 , or transition metal catalysis 6,9,10,[25][26][27][28][29][30] . Of particular note is the incompatibility of almost all these chiral catalytic systems with vinyl radical species in spite of their excellent and well-investigated reactivity towards hydrogen 31,32 , halogen 33,34 , and chalcogen 35 atom transfer.…”

Section: Main Textmentioning

confidence: 99%

Cu(I)-catalysed enantioselective chlorine atom transfer with vinyl radicals

Tang

Bian

Zhang

et al. 2023

Preprint

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Enantioselective intermolecular atom transfer reactions of vinyl radicals have hitherto remained elusive mainly due to their inherently high instability and reactivity which significantly compromises the stereodiscriminating substrate-catalyst interactions. Herein, we describe Cu(I)-catalyzed enantioselective chlorine atom transfer with vinyl radicals using tailormade tridentate anionic N,N,N-ligands featuring bulky peripheral substituents. This reaction readily accommodates (hetero)aryl and alkyl sulfonyl chlorides as radical precursors and more importantly, a large panel of 2-aminoaryl and 2-oxyaryl alkynes as substrates, providing highly transformable axially chiral vinyl chlorides in moderate to good yield with excellent enantioselectivity. The reaction can be easily scaled up to gram scales and straightforward manipulations of the thus obtained vinyl halides lead to axially chiral thiourea, pyridyl carboxamide, and quinolyl sulfonamide compounds, which are promising chiral reagents for asymmetric catalysis. Both experimental and theoretical mechanistic studies supported the proposed chlorine atom transfer reaction mechanism.

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Section: Main Textmentioning

confidence: 99%

Cu(I)-catalysed enantioselective chlorine atom transfer with vinyl radicals

Tang

Bian

Zhang

et al. 2023

Preprint

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Photocatalytic Site‐Selective Cascade Radical Addition of Biaryl Ynones for the Construction of Spiro‐ and Fused Carbon Rings

Liu,

Zhao,

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryFunctionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules. Ynones are good regional selectivity radical acceptors in organic synthesis, and many of bio‐relevant cyclic compounds could be easily obtained by direct radical cyclization reaction. Here, we report a photocatalytic cascade radical addition of biaryl ynones, for the divergent synthesis of privileged carbon cycles. Additionally, further transformation of the multi‐functional group product into a variety of other derivatives demonstrates the synthetic value of this developed method.

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Recent advances in sulfur/sulfonyl radical triggered cascade cyclization reactions of 1,n-enynes

Shi

Zhang

et al. 2023

Tetrahedron

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Recent advances in radical cascade cyclization of 1,n-enynes with trifluoromethylating agents

Cited by 3 publications

References 82 publications

Cu(I)-catalysed enantioselective chlorine atom transfer with vinyl radicals

Cu(I)-catalysed enantioselective chlorine atom transfer with vinyl radicals

Photocatalytic Site‐Selective Cascade Radical Addition of Biaryl Ynones for the Construction of Spiro‐ and Fused Carbon Rings

Recent advances in sulfur/sulfonyl radical triggered cascade cyclization reactions of 1,n-enynes

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