Recent Advances on 5-endo-Trig Radical Cyclization of All-Carbon Systems

doi:10.6023/cjoc202209029

Abstract

The 5-endo-trig radical closure has emerged as an ideal method for the fast aseembly of five-membered rings. It is believed to be kinetically disfavored due to the stereoelectronic disadvantages, so it is recognized as a disfavored process according to the Baldwin-Beckwith rules. Despite the challenges, continuous efforts have been devoted to develop effective strategies that enable 5-endo-trig radical cyclization. The recent advances on 5-endo-trig closure of 4-pentenyl radicals are summarized and the common strategies for accelerating the cyclization are analyzed, which will be valuable for the design and development of novel radical 5-endo-trig processes.

Key words: radical, 5-endo-trig cyclization, five-membered rings, conformational constraint, polar effect

Cite this article

Hanliang Zheng, Jingwen Su, Yulu Zhou, Gangguo Zhu. Recent Advances on 5-endo-Trig Radical Cyclization of All-Carbon Systems[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4060-4066.

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Fig. & Tab. 10

Scheme 1. Stereoelectronic effects of 5-endo-trig closure

Entry	R¹	R²	R³	Yield/%
Entry	R¹	R²	R³	2	3
1	ⁱPr	Me	H	0	88
2	ⁱBu	Me	H	52	33
3	Bn	Me	Me	7	72
4	H	Me	Me	73	14
5	Et	H	H	58	21

Table 1. Effect of substituents on the 5-endo-trig cyclization of bromomethyldimethylsilyl propargyl ethers.

Scheme 2. [2+2+1] radical cyclization of enynes

Scheme 3. [2+2+1] radical cyclization of 1,7-enynes and cycloalkanes

Scheme 4. [2+2+1] radical cyclization of 1,7-enynes with alkyl nitriles or acetones

Scheme 5. [2+2+1] radical cyclization of enynes with various radical precursors

Scheme 6. Persistent radical effect promoted 5-endo-trig radical cyclization.

Scheme 7. Traceless directing 5-endo sulfonylcarbocyclization of alkynes

Scheme 8. 5-endo-trifluoromethylcarbocyclization of ynones

Scheme 9. Radical [3+2] cycloaddition of alkyl aldehydes and alkynes

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全碳体系的5-endo-Trig自由基环化反应研究进展