Mn-Catalyzed Radical Brook Rearrangement/Alkenylation of α-Silyl Cyclobutanols

doi:10.6023/cjoc202604029

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (9): 3713-3721.DOI: 10.6023/cjoc202604029 Previous Articles Next Articles

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锰催化α-硅基环丁醇的自由基Brook重排/烯基化反应

李想^a, 张一智^b, 周刚^b, 刘晓磊^a^,^*(), 沈晓^b^,^c^,^*()

^a 济南大学智能材料与工程研究院济南 250022
^b 武汉大学高等研究院武汉 430072
^c 有机硅化合物及材料教育部工程研究中心武汉 430072

收稿日期:2026-04-21 修回日期:2026-05-13 发布日期:2026-05-27
通讯作者: 刘晓磊, 沈晓
基金资助:
国家重点研发计划(2022YFA1506100); 国家自然科学基金(22531010); 国家自然科学基金(22471201); 国家自然科学基金(21901191)

Mn-Catalyzed Radical Brook Rearrangement/Alkenylation of α-Silyl Cyclobutanols

Xiang Li^a, Yizhi Zhang^b, Gang Zhou^b, Xiaolei Liu^a^,^*(), Xiao Shen^b^,^c^,^*()

^a Institute for Smart Material & Engineering, University of Jinan, Jinan 250022
^b Institute for Advanced Studies, Wuhan University, Wuhan 430072
^c Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, Wuhan 430072

Received:2026-04-21 Revised:2026-05-13 Published:2026-05-27
Contact: Xiaolei Liu, Xiao Shen
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Key Research and Development Program of China(2022YFA1506100); National Natural Science Foundation of China(22531010); National Natural Science Foundation of China(22471201); National Natural Science Foundation of China(21901191)

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Abstract

A manganese-catalyzed radical Brook rearrangement/alkenylation cascade reaction of α-silyl cyclobutanols with 1,1-diarylalkenes is reported, enabling the synthesis of alkenylated cyclobutyl silyl ethers. This reaction exhibits excellent functional group tolerance and a broad substrate scope. Furthermore, scale-up experiments and synthetic applications demonstrate the potential utility of this strategy in organic synthesis.

Key words: manganese catalysis, alkenylation, radical Brook rearrangement, cyclobutanols

Cite this article

Xiang Li, Yizhi Zhang, Gang Zhou, Xiaolei Liu, Xiao Shen. Mn-Catalyzed Radical Brook Rearrangement/Alkenylation of α-Silyl Cyclobutanols[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3713-3721.

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Entry	Mn-cat	Ligand	n(1a)∶n(2a)	Solvent	Oxidant	Time/h	Yield/%
1	Mn(OAc)₂	—	1∶3	DCM	TBPB	12	14
2	Mn(acac)₃	—	1∶3	DCM	TBPB	12	6
3	MnBr₂	—	1∶3	DCM	TBPB	12	44
4	MnCl₂	—	1∶3	DCM	TBPB	12	Trace
5	MnS	—	1∶3	DCM	TBPB	12	Trace
6	MnI₂	—	1∶3	DCM	TBPM	12	Trace
7	MnBr₂	—	1∶3	DCM	TBPB	4	44
8	MnBr₂	—	1∶3	DCM	TBPM	4	50
9	MnBr₂	2,2-Bipyridine	1∶3	DCM	TBPM	4	10
10	MnBr₂	1,10-Phenanthroline	1∶3	DCM	TBPM	4	6
11	MnBr₂	BINAP	1∶3	DCM	TBPM	4	60
12	MnBr₂	XANTPHOS	1∶3	DCM	TBPM	4	46
13	MnBr₂	PPh₃	1∶3	DCM	TBPM	4	70
14^b	MnBr₂	PPh₃	1∶3	DCM	TBPM	6	82 (82)
15	MnBr₂	PPh₃	1∶3	DCM	TBPM	8	82
16	MnBr₂	PPh₃	1∶1	DCM	TBPM	6	58
17	MnBr₂	PPh₃	1∶2	DCM	TBPM	6	76
18	MnBr₂	PPh₃	1∶3.5	DCM	TBPM	6	70

Entry	Mn-cat	Ligand	n(1a)∶n(2a)	Solvent	Oxidant	Time/h	Yield/%
1	Mn(OAc)₂	—	1∶3	DCM	TBPB	12	14
2	Mn(acac)₃	—	1∶3	DCM	TBPB	12	6
3	MnBr₂	—	1∶3	DCM	TBPB	12	44
4	MnCl₂	—	1∶3	DCM	TBPB	12	Trace
5	MnS	—	1∶3	DCM	TBPB	12	Trace
6	MnI₂	—	1∶3	DCM	TBPM	12	Trace
7	MnBr₂	—	1∶3	DCM	TBPB	4	44
8	MnBr₂	—	1∶3	DCM	TBPM	4	50
9	MnBr₂	2,2-Bipyridine	1∶3	DCM	TBPM	4	10
10	MnBr₂	1,10-Phenanthroline	1∶3	DCM	TBPM	4	6
11	MnBr₂	BINAP	1∶3	DCM	TBPM	4	60
12	MnBr₂	XANTPHOS	1∶3	DCM	TBPM	4	46
13	MnBr₂	PPh₃	1∶3	DCM	TBPM	4	70
14^b	MnBr₂	PPh₃	1∶3	DCM	TBPM	6	82 (82)
15	MnBr₂	PPh₃	1∶3	DCM	TBPM	8	82
16	MnBr₂	PPh₃	1∶1	DCM	TBPM	6	58
17	MnBr₂	PPh₃	1∶2	DCM	TBPM	6	76
18	MnBr₂	PPh₃	1∶3.5	DCM	TBPM	6	70

锰催化α-硅基环丁醇的自由基Brook重排/烯基化反应

Mn-Catalyzed Radical Brook Rearrangement/Alkenylation of α-Silyl Cyclobutanols

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