Nickel-Catalyzed Stereoretentive Alkylcarbonylation of Alkenyl Triflates with Solid Alkylzinc Pivalates

doi:10.6023/cjoc202604052

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (7): 2713-2722.DOI: 10.6023/cjoc202604052 Previous Articles Next Articles

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镍催化烯基三氟甲磺酸酯立体保持的烷基羰基化反应

陈海鸿^a^,^†, 赵一譞^a^,^†, 林杰^a, 张潜^b^,^*(), 李杰^a^,^*()

^a 苏州大学材料与化学化工学部苏州市病原生物科学与抗感染医学重点实验室江苏苏州 215123
^b 西交利物浦大学理学院先进材料研究中心江苏苏州 215123

收稿日期:2026-04-30 修回日期:2026-06-04 发布日期:2026-06-26
作者简介:
†共同第一作者
基金资助:
国家自然科学基金(22322108); 国家自然科学基金(22571217); 江苏省自然科学基金(BK20231521); 苏州市科技计划(ZXL2024399)

Nickel-Catalyzed Stereoretentive Alkylcarbonylation of Alkenyl Triflates with Solid Alkylzinc Pivalates

Haihong Chen^a^,^†, Yixuan Zhao^a^,^†, Jie Lin^a, Qian Zhang^b^,^*(), Jie Li^a^,^*()

^a MOE Key Laboratory of Geriatric Diseases and Immunology, Suzhou Key Laboratory of Pathogen Bioscience and Anti-infective Medicine, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123
^b Department of Chemistry and Materials Science, Advanced Materials Research Center, School of Science, Xi'an-Jiaotong Liverpool University, Suzhou, Jiangsu 215123

Received:2026-04-30 Revised:2026-06-04 Published:2026-06-26
Contact: *E-mail: qian.zhang02@xjtlu.edu.cn;jjackli@suda.edu.cn
About author:
†(The authors contributed equally to this work).
Supported by:
National Natural Science Foundation of China(22322108); National Natural Science Foundation of China(22571217); Natural Science Foundation of Jiangsu Province(BK20231521); Science and Technology Program of Suzhou(ZXL2024399)

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Abstract

α,β-Unsaturated ketones are valuable prevalent skeletons in organic molecules, which can also be transformed to structurally diverse compounds. Thus far, the efficient construction of α,β-unsaturated ketones via transition-metal-catalyzed direct carbonylative cross-coupling strategies still suffer from limited substrate scope, particularly when constructing alkyl- alkenyl ketones. As such, we herein report a practical nickel-catalyzed stereoretentive carbonylation of tetrasubstituted alkenyl triflates with both primary and secondary alkylzinc pivalates under 101 kPa of CO gas. Moreover, this approach is distinguished by its mild conditions, simple operation, excellent stereoselectivity, and broad functional group compatibility, thereby providing an efficient method for the preparation of α,β-unsaturated ketones.

Key words: alkylcarbonylation, nickel catalyst, α,β-unsaturated ketones, alkylzinc pivalates

Cite this article

Haihong Chen, Yixuan Zhao, Jie Lin, Qian Zhang, Jie Li. Nickel-Catalyzed Stereoretentive Alkylcarbonylation of Alkenyl Triflates with Solid Alkylzinc Pivalates[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2713-2722.

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Fig. & Tab. 4

Scheme 1. State-of-art in the synthesis of α,β-unsaturated ketones via carbonylative cross-coupling strategy

Figure 1. Optimization studies for nickel-catalyzed carbonylative Negishi cross-coupling between alkenyl triflate 1a and alkylzinc pivalate 2a under 101 kPa of CO Reaction conditions: 1a (0.1 mmol, 1.0 equiv.), 2a (0.15 mmol, 1.5 equiv.), Ni(acac)2 (10.0 mol%), ligand (11.0 mol%), DMA (1.0 mL), 23 ℃, 12 h. a Without ligand. b Ni(acac)2 (5.0 mol%), L11 (6 mol%). c Ni(acac)2 (10.0 mol%), L5 (11 mol%). d Ni(acac)2 (10.0 mol%), L11 (11.0 mol%).

Table 1. Substrate scope of alkylzinc pivalates and tetrasubstituted alkenyl triflates for nickel-catalyzed carbonylative Negishi cross- couplinga

Scheme 2. Synthetic applications of the α,β-unsaturated ketone 3

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镍催化烯基三氟甲磺酸酯立体保持的烷基羰基化反应

Nickel-Catalyzed Stereoretentive Alkylcarbonylation of Alkenyl Triflates with Solid Alkylzinc Pivalates

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