碱性调控的选择性: 通过N-烷基-N-(2-(吡啶-2-基氨基)苯基)甲酰胺合成苯并咪唑酮和苯二氮䓬类化合物

doi:10.6023/cjoc202107062

有机化学 ›› 2022, Vol. 42 ›› Issue (4): 1146-1162.DOI: 10.6023/cjoc202107062 上一篇下一篇

研究论文

碱性调控的选择性: 通过N-烷基-N-(2-(吡啶-2-基氨基)苯基)甲酰胺合成苯并咪唑酮和苯二氮䓬类化合物

王玉斌^a, 郭成^b, 陶晟^a, 刘纪昌^a^,^c, 赵基钢^a^,^c, 刘宁^a^,^*(), 代斌^a^,^*()

a 石河子大学化学化工学院新疆兵团绿色化工过程重点实验室新疆石河子 832003
b 浙江大学医学院第二附属医院癌症研究所杭州 310009
c 华东理工大学化学工程学院上海 200237

收稿日期:2021-07-29 修回日期:2021-09-29 发布日期:2022-05-10
通讯作者: 刘宁, 代斌
基金资助:
兵团中青年科技创新领军人才计划项目(2020CB027); 石河子市中青年科技创新领军人才计划项目(2019RC01); 石河子大学大型贵重仪器设备共享测试基金资助项目.

Basicity-Tuned Selectivity: Synthesis of Benzimidazolone and Benzodiazepine from N-Alkyl-N-(2-(pyridin-2-ylamino)-phenyl)formamides

Yubin Wang^a, Cheng Guo^b, Sheng Tao^a, Jichang Liu^a^,^c, Jigang Zhao^a^,^c, Ning Liu^a(), Bin Dai^a()

a Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003
b Cancer Institute, The Second Affiliated Hospital Zhejiang University School of Medicine, Hangzhou 310009
c School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237

Received:2021-07-29 Revised:2021-09-29 Published:2022-05-10
Contact: Ning Liu, Bin Dai
Supported by:
Xinjiang Bingtuan Young and Middle-Aged Leading Scientists Program(2020CB027); Shihezi Young and Middle-Aged Leading Scientists Program(2019RC01); Open Sharing Fund for the Large-scale Instruments and Equipment of Shihezi University.

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摘要/Abstract

发展了一种碱控制选择性合成苯并咪唑酮和吡啶并苯二氮䓬衍生物的方法. 该方法以N-烷基-N-(2-(吡啶-2-基氨基)苯基)甲酰胺类化合物为原料, 以K₂S₂O₈为氧化剂, 当选用NaOAc为碱时, 高选择性地得到了一系列苯并咪唑酮衍生物; 当选用NaHCO₃为碱时, 得到了一系列吡啶并苯二氮䓬衍生物. 通过自由基捕捉实验的研究, 提出了相应可能的反应机理. 苯二氮䓬的克级放大实验和官能化衍生化实验说明该方法具有一定应用前景.

关键词: 苯并咪唑酮, 苯二氮䓬, 氧化剂诱导, 无金属

A base-controlled strategy for the selective preparation of benzimidazolone and pyrido-benzodiazepine derivatives was developed. The N-alkyl-N-(2-(pyridin-2-ylamino)phenyl)formamides underwent selective coupling to synthesize a series of benzimidazolones when NaOAc was used as bases and employed K₂S₂O₈ as oxidants. By changing bases to NaHCO₃, a series of benzodiazepines was obtained. The possible reaction mechanism was proposed based on the radical-trapping experiments. The applicability of this protocol is demonstrated by scale-up experiments and the functionalization of benzodiazepine products.

Key words: benzimidazolone, benzodiazepine, oxidant-induced, metal-free

引用此文

王玉斌, 郭成, 陶晟, 刘纪昌, 赵基钢, 刘宁, 代斌. 碱性调控的选择性: 通过N-烷基-N-(2-(吡啶-2-基氨基)苯基)甲酰胺合成苯并咪唑酮和苯二氮䓬类化合物[J]. 有机化学, 2022, 42(4): 1146-1162.

Yubin Wang, Cheng Guo, Sheng Tao, Jichang Liu, Jigang Zhao, Ning Liu, Bin Dai. Basicity-Tuned Selectivity: Synthesis of Benzimidazolone and Benzodiazepine from N-Alkyl-N-(2-(pyridin-2-ylamino)-phenyl)formamides[J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 1146-1162.

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Entry	2a, Condition A^a	2a, Condition B^b	3a, Condition C^c
1	2a, 80%; (3a, 0)	2a, 82%	3a, 68%; (2a, trace)
2	No K₂S₂O₈, 2a, 0 No base, 2a, 8%	No PhI(OAc)₂, 2a, 0	No K₂S₂O₈, 3a, 0 No base, 3a, trace
3	LiOt-Bu instead of NaOAc, 2a, 12% Na₂CO₃ instead of NaOAc, 2a, 10% KHCO₃ instead of NaOAc, 2a, trace K₂CO₃ instead of NaOAc, 2a, 11%	—	LiOt-Bu instead of NaHCO₃, 3a, 26% Na₂CO₃ instead of NaHCO₃, 3a, 29% KHCO₃ instead of NaHCO₃, 3a, 10% K₂CO₃ instead of NaHCO₃, 3a, 22%
4	DCE instead of MeCN, 2a, 30% DMSO instead of MeCN, 2a, 26% 1,4-Dioxane instead of MeCN, 2a, 35% MeCN/H₂O (V∶V=1∶1), 2a, 36%	DCE instead of MeCN, 2a, 69% DMSO instead of MeCN, 2a, 80% 1,4-Dioxane instead of MeCN, 2a, 77% MeCN/H₂O (V∶V=1∶1), 2a, 40%	DCE instead of MeCN, 3a, 40% DMSO instead of MeCN, 3a, 15% 1,4-Dioxane instead of MeCN, 3a, 10% MeCN/H₂O (V∶V=1∶1), 3a, 26%
5	Na₂S₂O₈ instead of K₂S₂O₈, 2a, 39% (NH₄)₂S₂O₈ instead of K₂S₂O₈, 2a, 45% DDQ instead of K₂S₂O₈, 2a, 0 TBHP instead of K₂S₂O₈, 2a, 0	Na₂S₂O₈ instead of PhI(OAc)₂, 2a, 0 (NH₄)₂S₂O₈ instead of PhI(OAc)₂, 2a, 0 DDQ instead of PhI(OAc)₂, 2a, 0 TBHP instead of PhI(OAc)₂, 2a, 0	Na₂S₂O₈ instead of K₂S₂O₈, 3a, 38% (NH₄)₂S₂O₈ instead of K₂S₂O₈, 3a, 32% DDQ instead of K₂S₂O₈, 3a, 0 TBHP instead of K₂S₂O₈, 3a, trace
6	K₂S₂O₈ (1.0 equiv.), 2a, 65% K₂S₂O₈ (1.5 equiv.), 2a, 80% K₂S₂O₈ (2.0 equiv.), 2a, 79%	PhI(OAc)₂ (1.0 equiv.), 2a, 47% PhI(OAc)₂ (1.5 equiv.), 2a, 82% PhI(OAc)₂ (2.0 equiv.), 2a, 84%	K₂S₂O₈ (1.0 equiv.), 3a, 36% K₂S₂O₈ (1.5 equiv.), 3a, 61% K₂S₂O₈ (2.0 equiv.), 3a, 23%
7	NaOAc (1.5 equiv.), 2a, 69% NaOAc (2.0 equiv.), 2a, 80% NaOAc (3.0 equiv.), 2a, 78%	—	NaHCO₃ (1.5 equiv.), 3a, 61% NaHCO₃ (2.0 equiv.), 3a, 69% NaHCO₃ (3.0 equiv.), 3a, 67%
8	100 ℃ instead of 80 ℃, 2a, 80% 50 ℃ instead of 80 ℃, 2a, 58%	50 ℃ instead of r.t., 2a, 85%	100 ℃ instead of 80 ℃, 3a, 65% 50 ℃ instead of 80 ℃, 3a, 47%
9	—	—	Air, 3a, 59%
10	48 h, 2a, 80%	5 h, 2a, 80%	48 h, 3a, 65%

Entry	2a, Condition A^a	2a, Condition B^b	3a, Condition C^c
1	2a, 80%; (3a, 0)	2a, 82%	3a, 68%; (2a, trace)
2	No K₂S₂O₈, 2a, 0 No base, 2a, 8%	No PhI(OAc)₂, 2a, 0	No K₂S₂O₈, 3a, 0 No base, 3a, trace
3	LiOt-Bu instead of NaOAc, 2a, 12% Na₂CO₃ instead of NaOAc, 2a, 10% KHCO₃ instead of NaOAc, 2a, trace K₂CO₃ instead of NaOAc, 2a, 11%	—	LiOt-Bu instead of NaHCO₃, 3a, 26% Na₂CO₃ instead of NaHCO₃, 3a, 29% KHCO₃ instead of NaHCO₃, 3a, 10% K₂CO₃ instead of NaHCO₃, 3a, 22%
4	DCE instead of MeCN, 2a, 30% DMSO instead of MeCN, 2a, 26% 1,4-Dioxane instead of MeCN, 2a, 35% MeCN/H₂O (V∶V=1∶1), 2a, 36%	DCE instead of MeCN, 2a, 69% DMSO instead of MeCN, 2a, 80% 1,4-Dioxane instead of MeCN, 2a, 77% MeCN/H₂O (V∶V=1∶1), 2a, 40%	DCE instead of MeCN, 3a, 40% DMSO instead of MeCN, 3a, 15% 1,4-Dioxane instead of MeCN, 3a, 10% MeCN/H₂O (V∶V=1∶1), 3a, 26%
5	Na₂S₂O₈ instead of K₂S₂O₈, 2a, 39% (NH₄)₂S₂O₈ instead of K₂S₂O₈, 2a, 45% DDQ instead of K₂S₂O₈, 2a, 0 TBHP instead of K₂S₂O₈, 2a, 0	Na₂S₂O₈ instead of PhI(OAc)₂, 2a, 0 (NH₄)₂S₂O₈ instead of PhI(OAc)₂, 2a, 0 DDQ instead of PhI(OAc)₂, 2a, 0 TBHP instead of PhI(OAc)₂, 2a, 0	Na₂S₂O₈ instead of K₂S₂O₈, 3a, 38% (NH₄)₂S₂O₈ instead of K₂S₂O₈, 3a, 32% DDQ instead of K₂S₂O₈, 3a, 0 TBHP instead of K₂S₂O₈, 3a, trace
6	K₂S₂O₈ (1.0 equiv.), 2a, 65% K₂S₂O₈ (1.5 equiv.), 2a, 80% K₂S₂O₈ (2.0 equiv.), 2a, 79%	PhI(OAc)₂ (1.0 equiv.), 2a, 47% PhI(OAc)₂ (1.5 equiv.), 2a, 82% PhI(OAc)₂ (2.0 equiv.), 2a, 84%	K₂S₂O₈ (1.0 equiv.), 3a, 36% K₂S₂O₈ (1.5 equiv.), 3a, 61% K₂S₂O₈ (2.0 equiv.), 3a, 23%
7	NaOAc (1.5 equiv.), 2a, 69% NaOAc (2.0 equiv.), 2a, 80% NaOAc (3.0 equiv.), 2a, 78%	—	NaHCO₃ (1.5 equiv.), 3a, 61% NaHCO₃ (2.0 equiv.), 3a, 69% NaHCO₃ (3.0 equiv.), 3a, 67%
8	100 ℃ instead of 80 ℃, 2a, 80% 50 ℃ instead of 80 ℃, 2a, 58%	50 ℃ instead of r.t., 2a, 85%	100 ℃ instead of 80 ℃, 3a, 65% 50 ℃ instead of 80 ℃, 3a, 47%
9	—	—	Air, 3a, 59%
10	48 h, 2a, 80%	5 h, 2a, 80%	48 h, 3a, 65%

碱性调控的选择性: 通过N-烷基-N-(2-(吡啶-2-基氨基)苯基)甲酰胺合成苯并咪唑酮和苯二氮䓬类化合物

Basicity-Tuned Selectivity: Synthesis of Benzimidazolone and Benzodiazepine from N-Alkyl-N-(2-(pyridin-2-ylamino)-phenyl)formamides

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