Copper-catalyzed regioselective 1,4-sulfonylcyanation of 1,3-enynes with sulfonyl chlorides and TMSCN

Lv, Yunhe; Han, Wanru; Pu, Weiya; Xie, Jianghui; Wang, Axue; Zhang, Mengyue; Wang, Jin; Lai, Junrong

doi:10.1039/d2qo00486k

Cited by 16 publications

(7 citation statements)

References 53 publications

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“…Enynes ( 1c , 1i , and 1n–1t ) were synthesized following the literature procedures . Substrates 1b , 1d–1h , 1j–1m , and 9 have been reported in our previous study …”

Section: Methodsmentioning

confidence: 99%

Metal-Free Highly Regioselective 1,4-Sulfonyliodination of 1,3-Enynes

Lai

et al. 2023

J. Org. Chem.

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Herein, a novel, practical, and green synthetic method using readily available 1,3-enynes with sulfonyl hydrazides and I2 through tert-butyl hydroperoxide (TBHP)-mediated 1,4-sulfonyliodination has been developed for synthesizing various tetrasubstituted allenyl iodides under metal-free conditions. Notably, the proposed method exhibits a broad substrate scope, operational simplicity, tolerance to air, high functional-group tolerance, satisfactory yields, and excellent regioselectivity as well as involves the use of cost-effective reagents such as green oxidants.

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“…Enynes ( 1c , 1i , and 1n–1t ) were synthesized following the literature procedures . Substrates 1b , 1d–1h , 1j–1m , and 9 have been reported in our previous study …”

Section: Methodsmentioning

confidence: 99%

Metal-Free Highly Regioselective 1,4-Sulfonyliodination of 1,3-Enynes

Lai

et al. 2023

J. Org. Chem.

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“…On the other hand, in the presence of sulfonyl chlorides, TMSCN and copper catalyst, a 1,4-sulfonylcyanation rather than 1,4-addition of sulfonyl halide would occur, leading to a range of 5-sulfonylpenta-2,3-dienenitrile derivatives with good func- tional group tolerance and regioselectivity (Scheme 6). [17] Furthermore, not only aryl sulfonyl chlorides but also alkyl sulfonyl chlorides participated in this reaction smoothly. A possible mechanism involving sulfonyl and allenyl radical was proposed as shown in Scheme 6.…”

Section: Transition-metal-catalyzed Reactions Involving Allenyl Radicalsmentioning

confidence: 96%

Allenyl Radicals in Organic Synthesis: Challenges and Recent Advances

Zhang

2022

Eur J Org Chem

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Allenyl radicals are rarely employed as intermediates for the synthesis of allenes probably owe to the lack of convenient methods for their generation and the high reactivity of short‐lived allenyl radicals. However, strategies take advantage of allenyl radicals are considered as a significant complement to reactions which couldn't proceed via an allenyl ionic pathway. As a result, several important methods have been developed in the past decades. Herein, this review is aimed to summarize the recent advance in reactions involving allenyl radicals by highlighting some outstanding challenges and confirming potential areas of improvement, which would offer an inspiration for future studies

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“…Recently, Lv and colleagues developed a Cu-catalyzed 1,4-sulfonylcyanation reaction of 1,3-enynes with alkyl or aryl sulfonyl chlorides and TMSCN ( Scheme 18 ) [ 50 ]. Under the catalysis of Cu(CH 3 CN) 4 PF 6 , sulfonyl-containing allenic nitriles 17 were obtained in good yields and high regioselectivity.…”

Section: 14-difunctionalization Reactionsmentioning

confidence: 99%

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Zhang

2023

Molecules

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Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction of functional groups. In radical difunctionalization reactions, the radicals in the first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, and ring opening. The resulting radical intermediates can undertake the following paths for the second functionalization: (1) couple with other radical groups, (2) oxidize to cations and then react with nucleophiles, (3) reduce to anions and then react with electrophiles, (4) couple with metal-complexes. The rearrangements of radicals provide the opportunity for the synthesis of 1,3-, 1,4-, 1,5-, 1,6-, and 1,7-difunctionalization products. Multiple ways to initiate the radical reaction coupling with intermediate radical rearrangements make the radical reactions good for difunctionalization at the remote positions. These reactions offer the advantages of synthetic efficiency, operation simplicity, and product diversity.

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Copper-catalyzed regioselective 1,4-sulfonylcyanation of 1,3-enynes with sulfonyl chlorides and TMSCN

Abstract: A novel and practical copper-catalyzed reaction for the 1,4-sulfonylcyanation of 1,3-enynes under mild conditions is described. This protocol provides efficient and straightforward access to a variety of 5-sulfonylpenta-2,3-dienenitrile derivatives with...

Cited by 16 publications

References 53 publications

Metal-Free Highly Regioselective 1,4-Sulfonyliodination of 1,3-Enynes

Metal-Free Highly Regioselective 1,4-Sulfonyliodination of 1,3-Enynes

Allenyl Radicals in Organic Synthesis: Challenges and Recent Advances

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

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