钯催化烯基苯并噁嗪酮基于内球型机理的线性和不对称烯丙基烷基化反应

doi:10.1016/S1872-2067(20)63751-2

催化学报 ›› 2021, Vol. 42 ›› Issue (7): 1227-1237.DOI: 10.1016/S1872-2067(20)63751-2

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钯催化烯基苯并噁嗪酮基于内球型机理的线性和不对称烯丙基烷基化反应

王凯^a^,^b, 王彬力^b^,^c, 刘相慧^a^,^b, 樊红军^c^,^*(), 刘龑^a^,^#(), 李灿^a^,^$()

^a中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连116023
^b中国科学院大学, 北京100049
^c中国科学院大连化学物理研究所, 分子反应动力学国家重点实验室, 辽宁大连116023

收稿日期:2020-10-28 接受日期:2020-12-15 出版日期:2021-07-18 发布日期:2021-01-19
通讯作者: 樊红军,刘龑,李灿
基金资助:
国家自然科学基金(21673224);国家自然科学基金(21871254);国家自然科学基金(21532006);国家自然科学基金(21472187);大连化学物理研究所(DICP ZZBS201602);中国科学院战略科技先导专项(XDB17010200)

Palladium-catalyzed enantioselective linear allylic alkylation of vinyl benzoxazinanones: An inner-sphere mechanism

Kai Wang^a^,^b, Binli Wang^b^,^c, Xianghui Liu^a^,^b, Hongjun Fan^c^,^*(), Yan Liu^a^,^#(), Can Li^a^,^$()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cState Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2020-10-28 Accepted:2020-12-15 Online:2021-07-18 Published:2021-01-19
Contact: Hongjun Fan,Yan Liu,Can Li
About author:^$ Tel: +86-411-84379070; Fax: +86-411-84694447; E-mail: canli@dicp.ac.cn
^# Tel: +86-411-84379252; Fax: +86-411-84694447; E-mail: yanliu503@dicp.ac.cn;
^* Tel: +86-411-84379913; Fax: +86-411-84675584; E-mail: fanhj@dicp.ac.cn;
Supported by:
National Natural Science Foundation of China(21673224);National Natural Science Foundation of China(21871254);National Natural Science Foundation of China(21532006);National Natural Science Foundation of China(21472187);Dalian Institute of Chemical Physics(DICP ZZBS201602);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17010200)

摘要/Abstract

摘要：

烯基苯并噁嗪酮作为底物参与反应受到有机合成工作者的广泛关注. 在过渡金属催化作用下, 烯基苯并噁嗪酮脱除一分子二氧化碳, 生成的两性离子中间体既可以被亲核试剂进攻, 得到结构丰富的芳香胺, 也可以作为1,4-偶极子与硫叶立德, 缺电子烯烃或α,β-不饱和醛参与成环, 分别生成相应的五元、六元或七元含氮杂环. 后者广泛存在于农药、医药和生物活性分子中. 已报道的钯催化烯基苯并噁嗪酮的不对称转化反应中, 支链结构是主产物, 线性结构产物比较少见. 这是因为烯丙基邻位的氨基负离子与亲核试剂存在氢键或者静电作用, 诱导亲核试剂进攻位阻更大但是能量更低的苄位. 不同于传统的钯催化烯丙基取代反应, 产物的结构通常是由亲核试剂的软硬程度决定. 除了化学选择性的问题, 产物中双键的Z/E构型和立体选择性的控制也同样成为挑战. 近期Li课题组(Org. Lett., 2016, 18, 4392-4395)基于定位基辅助的Rh(III)催化C‒H活化策略实现了芳烃烯丙基化得到线性产物. Shi课题组(Chem. Commun., 2019, 55, 1283-1286)利用Ir(I)和Brönsted酸协同催化实现了吖内酯进攻端位烯丙基. 但是, 这些反应仅能得到消旋产物. 发展不对称的线性烯丙基取代反应, 不仅可以拓展烯基苯并噁嗪酮的应用前景, 还可以合成具有手性的邻乙烯基芳香胺.
本文采用α-硫氰基取代的茚酮作亲核试剂, 不同于以往文献报道的机理, 氨基负离子对烯醇式茚酮没有起到导向作用, 意外得到以直链为主的产物. 经过优化, 最终以联萘二酚骨架亚膦酰胺为配体, 钯作为催化剂, 成功构建了一系列与硫氰基直接相连的季碳手性产物. 所有反应产物均有优秀的化学选择性(线性选择性> 20/1), E/Z选择性(> 20/1)和立体选择性(最高95% ee). 并且该反应适用范围广泛, 基团的兼容性良好. 为解释实验结果, 本文进行相关的控制实验和DFT计算. 计算结果表明, 由于氨基负离子碱性较强, 茚酮α位C‒H酸性较强, 直接发生了质子转移生成茚酮烯醇负离子, 此时氢键作用消失不能起到导向作用. 本文还考察了茚酮烯醇负离子与烯丙基钯通过静电作用形成离子复合物. 与之前文献报道不同, 本文采用了单齿膦配体且钯与配体等量, 这意味着钯处于配位不饱和状态, 导致离子复合物极其不稳定, 烯醇负离子与硫氰基直接与钯配位成键, 该过程结合能高达23.47 kcal/mol. 最终配合物中间体通过内球型机理, 经历环状过渡态得到以线性为主的产物.

关键词: 钯催化, 不对称催化, 烯丙基烷基化, 烯基苯并噁嗪酮, 内球型机理

Abstract:

Palladium-catalyzed asymmetric allylic alkylation (AAA) of vinyl benzoxazinanones has become an important strategy for the synthesis of chiral nitrogen-containing heterocycle compounds. However, the asymmetric synthesis of linear-selective products has rarely been reported. The simultaneous control of regio-, E/Z- and enantioselectivities constitutes a major challenge and inhibits the advancement of this chemistry. Herein, we present a palladium-catalyzed AAA of vinyl benzoxazinanones with α-thiocyanato ketones, affording various chiral thiocyanates characterized with high linear-, E- and stereoselectivities. The reaction has a broad substrate scope and the chiral thiocyanates can be transformed to useful heterocycles. Experimental and computational studies suggest an inner-sphere mechanism for AAA process, which results from the acidic and coordination effect of the nucleophilic substrates with palladium catalyst.

Key words: Pd catalysis, Asymmetric catalysis, Allylic alkylation, Vinyl benzoxazinanones, Inner-sphere mechanism

王凯, 王彬力, 刘相慧, 樊红军, 刘龑, 李灿. 钯催化烯基苯并噁嗪酮基于内球型机理的线性和不对称烯丙基烷基化反应[J]. 催化学报, 2021, 42(7): 1227-1237.

Kai Wang, Binli Wang, Xianghui Liu, Hongjun Fan, Yan Liu, Can Li. Palladium-catalyzed enantioselective linear allylic alkylation of vinyl benzoxazinanones: An inner-sphere mechanism[J]. Chinese Journal of Catalysis, 2021, 42(7): 1227-1237.

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图/表 8

Scheme 1. The chemistry of vinyl benzoxazinanones.

Table 1 Optimization of reaction conditions a.


Entry	Ligand	Solvent	t (h)	Yield ^b (%)	ee ^c (%)
1	L1	DCM	3.0	48	85
2	L2	DCM	1.5	69	60
3	L3	DCM	1.5	57	53
4	L4	DCM	3.5	15	‒24
5	L5	DCM	12	trace	—
6	L6	DCM	12	trace	—
7	L7	DCM	12	trace	—
8	L1	THF	3.0	26	83
9	L1	MeOH	3.0	trace	—
10	L1	CHCl₃	3.0	42	84
11	L1	toluene	3.0	57	86
12	L1	CH₃CN	3.0	38	84
13	L1	DCE	3.0	50	87
14 ^d	L1	DCE	3.0	29	89
15 ^e	L1	DCE	3.0	35	80
16 ^f	L1	DCE	24	70	91

Scheme 2 Substrate scope of vinyl benzoxazinanones 1 and α-thiocyanato ketones 2. Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), Pd2(dba)3·CHCl3 (5 mol%), chiral ligand L1 (11 mol%) and K2CO3 (2.0 equiv.) in 2 mL DCE at 0 °C for 24 h, isolated yields. a 4.0 equiv. K2CO3 was employed.

Scheme 3. Control experiments.

Fig. 1. Three possible reaction models proposed for this allylic alkylation reaction. Model A: hydrogen bond direction. Model B: ion pair intermediate. Model C: α-thiocyanato ketone coordinated π-allyl Pd complex.

Fig. 2. The reaction energy profile for the Pd(0)-catalyzed allylic substitution with α-thiocyanato ketones through inner-sphere mechanism. Energies are the free energies in DCE in kcal/mol, and bond lengths are in ?. The hydrogens attached on carbon atoms was omitted for clarity.

Scheme 4. Substrate scope of α-acyl indanones. Reaction conditions: 1a (0.1 mmol or 0.05 mmol), 8 (1.5 equiv.), Pd2(dba)3·CHCl3 (5 mol%), chiral ligand L1 (11 mol%) and K2CO3 (2.0 equiv.) in DCE (1.0 mL or 0.5 mL) at 0 °C for 4 h, isolated yields.

Scheme 5. Synthetic utility.

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钯催化烯基苯并噁嗪酮基于内球型机理的线性和不对称烯丙基烷基化反应

Palladium-catalyzed enantioselective linear allylic alkylation of vinyl benzoxazinanones: An inner-sphere mechanism

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