光催化甲苯衍生物、环烷烃与无机亚磺酸盐的位点选择性C(sp3)-H砜基化

doi:10.1016/S1872-2067(21)63953-0

催化学报 ›› 2022, Vol. 43 ›› Issue (3): 564-570.DOI: 10.1016/S1872-2067(21)63953-0

• 可见光催化有机合成专栏 • 上一篇下一篇

光催化甲苯衍生物、环烷烃与无机亚磺酸盐的位点选择性C(sp³)-H砜基化

张少南, 曹石, 林玉妹, 沙利源, 陆成, 龚磊^*()

厦门大学化学化工学院, 福建省化学生物学重点实验室, 福建厦门 361005

收稿日期:2021-09-02 修回日期:2021-09-02 接受日期:2021-10-02 出版日期:2022-03-18 发布日期:2022-02-18
通讯作者: 龚磊
基金资助:
国家自然科学基金(22071209);国家自然科学基金(22071206);国家万人计划青年拔尖人才支持计划;福建省杰出青年基金(2017J06006);中央高校基础研究基金(20720190048);教育部基础学科拔尖学生培养计划

Photocatalyzed site-selective C(sp3)‒H sulfonylation of toluene derivatives and cycloalkanes with inorganic sulfinates

Shaonan Zhang, Shi Cao, Yu-Mei Lin, Liyuan Sha, Cheng Lu, Lei Gong^*()

Key Laboratory of Chemical Biology of Fujian Province, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2021-09-02 Revised:2021-09-02 Accepted:2021-10-02 Online:2022-03-18 Published:2022-02-18
Contact: Lei Gong
Supported by:
National Natural Science Foundation of China(22071209);National Natural Science Foundation of China(22071206);National Youth Talent Support Program;Natural Science Foundation of Fujian Province of China(2017J06006);Fundamental Research Funds for the Central Universities(20720190048);Basic Disciplines Training Program for Top-notch Students of the Ministry of Education.

摘要/Abstract

摘要：

烃类是最基础的有机分子之一, 具有品种丰富、来源广泛、价格低廉等优势, 其多样性、选择性转化一直备受合成化学家关注. 然而, 这些化合物中通常存在多个键能高、极性低、相互间差异性小的C(sp³)‒H键, 因此, 实现高效、选择性C‒H官能化极具挑战性.
近年来, 可见光催化广泛应用于有机合成中, 与氢转移催化相结合所发展的可见光氢转移光催化策略在C(sp³)‒H官能化反应中展现了较大的潜力, 特别是为化学、位点、立体选择性等问题的解决带来了新机遇. 尽管如此, 能在激发态有效切断烷烃、环烷烃等中未活化的C(sp³)‒H键, 被用于直接氢转移光催化的催化剂种类很少, 主要局限于十钨酸盐、芳香酮衍生物等, 因此, 发展新型氢转移光催化剂和新反应具有重要意义.
近期人们发现, 一种共轭多元醌分子(5,7,12,14-并五苯四酮, PT)具有较好的光物理性质、电化学性能及溶解性, 可被用作直接氢转移光催化剂. 为了深入研究其催化活性及在惰性烃类化合物转化中的应用, 本文利用PT与铜盐协同作用, 开发了一种高效、高选择性的C(sp³)‒H砜基化反应, 以无机亚磺酸盐作为砜基化试剂, 将一系列甲苯衍生物、环烷烃、药物类似物等转化为具有潜在生物活性和重要合成应用的砜类产物. 该反应条件温和、操作简单, 不需要使用贵金属催化剂和配体, 反应原料均已商品化且价格较便宜. 通过自由基淬灭与捕获、自由基钟、控制实验、荧光淬灭等机理实验, 证明了反应的自由基历程和铜介导的金属有机过程. X射线光电子能谱证明过程中伴随着零价铜的产生, 反应仅需要1.2当量的二价铜盐作为氧化剂, 为多样性C‒H官能化反应提出了新的策略和路径. 此外, 该方法还成功应用于药物类似物的后期官能化, 展现了良好的官能团兼容性和位点选择性, 进一步证明了其应用价值.
综上所述, 本文以一种商品化的共轭多元醌作为直接氢转移光催化剂, 铜盐为氧化剂, 无机亚磺酸盐为砜基化试剂, 开发了一种经济低毒、温和易操作的甲苯衍生物、环烷烃C(sp³)‒H官能化新方法, 为砜类化合物的合成与开发利用提供了高效、高选择性的途径, 也为药物分子后期官能化提供了有效的手段.

关键词: 可见光, 光催化, C(sp³)-H官能化, 砜基化, 自由基

Abstract:

The development of practical methods for the direct and selective C(sp³)‒H functionalization of hydrocarbons is an attractive topic in synthetic chemistry. Although the radical-mediated hydrogen atom transfer (HAT) process has shown considerable potential in such reactions, it still faces fundamental problems associated with reactivity and selectivity. Herein, we report a convenient and economic approach to site-selective C(sp³)‒H sulfonylation via photo-induced HAT catalysis. Employing a conjugated polycyclic quinone as a direct HAT photocatalyst, commercially available inorganic sulfinates as the sulfonylation source, copper triflate as an inexpensive oxidant, a variety of toluene derivatives and cycloalkanes were converted into biologically and synthetically interesting sulfone products under mild conditions. The mechanistic studies reveal that the reaction sequence involves direct HAT-induced radical formation and a subsequent copper-mediated organometallic process for the C‒S bond formation. This method offers an appealing opportunity to furnish high value-added products from abundant hydrocarbon starting materials and inexpensive reagents.

Key words: Visible light, Photocatalysis, C(sp³)-H functionalization, Sulfonylation, Radical

张少南, 曹石, 林玉妹, 沙利源, 陆成, 龚磊. 光催化甲苯衍生物、环烷烃与无机亚磺酸盐的位点选择性C(sp³)-H砜基化[J]. 催化学报, 2022, 43(3): 564-570.

Shaonan Zhang, Shi Cao, Yu-Mei Lin, Liyuan Sha, Cheng Lu, Lei Gong. Photocatalyzed site-selective C(sp3)‒H sulfonylation of toluene derivatives and cycloalkanes with inorganic sulfinates[J]. Chinese Journal of Catalysis, 2022, 43(3): 564-570.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63953-0

https://www.cjcatal.com/CN/Y2022/V43/I3/564

图/表 7

Scheme 1. (a) Representative aryl sulfone-based bioactive molecules; (b) Overview of this work.

Table 1 Optimization of the reaction conditions a.

Entry	Metal salt	PC	T (°C)	Yield ^b (%)
1	Cu(ClO₄)₂∙6H₂O	PC1	20	39
2	Ni(ClO₄)₂∙6H₂O	PC1	20	5
3	Co(ClO₄)₂∙6H₂O	PC1	20	trace
4	Zn(ClO₄)₂∙6H₂O	PC1	20	trace
5	Fe(ClO₄)₂∙H₂O	PC1	20	11
6	CuCl₂∙2H₂O	PC1	20	43
7	CuSO₂∙5H₂O	PC1	20	31
8	Cu(OTf)₂	PC1	20	74
9 ^c	Cu(OTf)₂	PC1	20	71
10 ^d	Cu(OTf)₂	PC1	20	76
11	Cu(OTf)₂	PC2	20	45
12	Cu(OTf)₂	PC3	20	32
13	Cu(OTf)₂	PC4	20	0
14	Cu(OTf)₂	PC1	40	55
15	Cu(OTf)₂	PC1	0	40
16	none	PC1	20	0
17 ^e	none	PC1	20	trace
18 ^f	none	PC1	20	trace
19 ^g	none	PC1	20	trace
20	Cu(OTf)₂	none	20	0
21 ^h	Cu(OTf)₂	PC1	20	0
22 ⁱ	Cu(OTf)₂	PC1	20	trace

Scheme 2. Scope of toluene derivatives and sulfinates. a Reaction in a 1.0 mmol scale.

Scheme 3. C(sp3)-H sulfonylation of cycloalkanes and late-stage functionalization of celestolide.

Scheme 4. (a) Radical trapping experiments; (b) Radical clock experiments; (c) Reactions interfered by other nucleophiles; (d) Direct reaction with a copper sulfinate complex.

Fig. 1. (a) Emission quenching of PC1 with 1-ethyl-naphthalene (1 g); (b) Stern-Volmer plots. I0 and I are respective luminescence intensities in the absence and presence of the indicated concentrations of the corresponding quencher.

Scheme 5. Proposed reaction mechanism.

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光催化甲苯衍生物、环烷烃与无机亚磺酸盐的位点选择性C(sp³)-H砜基化

Photocatalyzed site-selective C(sp3)‒H sulfonylation of toluene derivatives and cycloalkanes with inorganic sulfinates

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