Zirconium Lewis Acid-Catalyzed de Mayo-Type Ring Expansion of Cyclic β-Dicarbonyls

doi:10.6023/cjoc202607015

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (9): 3594-3602.DOI: 10.6023/cjoc202607015 Previous Articles Next Articles

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锆路易斯酸催化的环状β-二羰基化合物的de Mayo型扩环反应

王钧锋^a, 刘芮碹^a, 米学玲^a^,^*(), 罗三中^b

^a 北京师范大学化学学院北京 100875
^b 清华大学化学系基础分子科学中心北京 100084

收稿日期:2026-07-15 修回日期:2026-07-31 发布日期:2026-08-21
通讯作者: 米学玲
基金资助:
国家自然科学基金(22393891); 及国家重点研发计划(2023YFA1506401); 及国家重点研发计划(2023YFA1506402)

Zirconium Lewis Acid-Catalyzed de Mayo-Type Ring Expansion of Cyclic β-Dicarbonyls

Junfeng Wang^a, Ruixuan Liu^a, Xueling Mi^a^,^*(), Sanzhong Luo^b

^a College of Chemistry, Beijing Normal University, Beijing 100875
^b Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084

Received:2026-07-15 Revised:2026-07-31 Published:2026-08-21
Contact: Xueling Mi
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Natural Science Foundation of China(22393891); National Key R&D Program of China(2023YFA1506401); National Key R&D Program of China(2023YFA1506402)

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Abstract

Zirconium-Lewis acid was developed to facilitate a de Mayo-type ring expansion reaction in the absence of external photosensitizers and additives. The reaction proceeds through a [2＋2] cycloaddition and retro-aldol reaction sequence between cyclic β-ketocarbonyls and alkenes, which are compatible with various substrates in good yields. Through this strategy, a series of functionalized medium sized-ring skeletons can be constructed starting from readily available starting materials.

Key words: de Mayo reaction, ring expansion, zirconium Lewis acid-catalysis, β-ketocarbonyls

Cite this article

Junfeng Wang, Ruixuan Liu, Xueling Mi, Sanzhong Luo. Zirconium Lewis Acid-Catalyzed de Mayo-Type Ring Expansion of Cyclic β-Dicarbonyls[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3594-3602.

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Fig. & Tab. 5

References 22

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Entry	Variation from the initial condition	Yield^a/%
1	None	50
2	ZrSO₄ instead of ZrCl₄	n.r.
3	Sc(OTf)₃, HfCl₄ instead of ZrCl₄	34, 42
4	DCM, toluene instead of CH₃CN	57, 60
5	CH₃CN/Toluene (1.0/1.0 mL) instead of CH₃CN	83
6	CH₃CN/Toluene (1.6/0.4 mL) instead of CH₃CN, 2.0 equiv. 2a	91 (78^b)
7	400 nm, 450 nm	38, trace
8	Additive (0.5 equiv.), K₂CO₃, NEt₃	42, 48
9	w/o ZrCl₄	n.r
10	w/o light or under air	n.r.

Entry	Variation from the initial condition	Yield^a/%
1	None	50
2	ZrSO₄ instead of ZrCl₄	n.r.
3	Sc(OTf)₃, HfCl₄ instead of ZrCl₄	34, 42
4	DCM, toluene instead of CH₃CN	57, 60
5	CH₃CN/Toluene (1.0/1.0 mL) instead of CH₃CN	83
6	CH₃CN/Toluene (1.6/0.4 mL) instead of CH₃CN, 2.0 equiv. 2a	91 (78^b)
7	400 nm, 450 nm	38, trace
8	Additive (0.5 equiv.), K₂CO₃, NEt₃	42, 48
9	w/o ZrCl₄	n.r
10	w/o light or under air	n.r.

锆路易斯酸催化的环状β-二羰基化合物的de Mayo型扩环反应

Zirconium Lewis Acid-Catalyzed de Mayo-Type Ring Expansion of Cyclic β-Dicarbonyls

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References 22

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