Transition-Metal-Free Regioselective Thiocyanation of Triisopropylsilane (TIPS)-Protected Phenols

doi:10.6023/cjoc202307015

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (4): 1327-1336.DOI: 10.6023/cjoc202307015 Previous Articles Next Articles

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三异丙基硅烷(TIPS)保护苯酚的无过渡金属催化区域选择性硫氰化反应

鞠国栋^a, 周冠宇^a, 赵应声^a^,^b^,^*()

a 苏州大学材料与化学化工学部江苏苏州 215123
b 河南师范大学化学化工学院河南新乡 453000

收稿日期:2023-07-15 修回日期:2023-09-12 发布日期:2023-11-23
基金资助:
国家自然科学基金(22171197); 江苏省高等学校自然科学基金重大基础研究项目(21KJA150002); 环保功能吸附材料制备技术国地联合工程实验室开放课题(SDGC2121); 江苏高校优势学科建设工程; 河南师范大学化学化工学院开放基金资助项目.

Transition-Metal-Free Regioselective Thiocyanation of Triisopropylsilane (TIPS)-Protected Phenols

Guodong Ju^a, Guangyu Zhou^a, Yingsheng Zhao^a^,^b()

a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123
b School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453000

Received:2023-07-15 Revised:2023-09-12 Published:2023-11-23
Contact: * E-mail: yszhao@suda.edu.cn
Supported by:
National Natural Science Foundation of China(22171197); Major Basic Research Project of the Natural Science Foundation of Jiangsu Higher Education Institutions(21KJA150002); National Local Joint Engineering Laboratory to Functional Adsorption Material Technology for Environmental Protection(SDGC2121); Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD); Open Research Fund of the School of Chemistry and Chemical Engineering, Henan Normal University

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Abstract

Arylthiocyanate compounds are crucial in organic chemistry. They have widespread applications in agrochemicals, pharmaceuticals, and materials chemistry. Herein, the transition metal-free regioselective thiocyanation of triisopropylsilane (TIPS)-protected phenol derivatives was achieved using NH₄SCN as thiocyanation reagent and potassium peroxymonosulfonate/(2KHSO₅•KHSO₄•K₂SO₄, oxone) as the oxidant. The conversion was achieved in good to excellent yields under mild reaction conditions. Further, various functional groups were well tolerated in these reaction conditions. The practicability of this method was demonstrated in the thiocyanation of bioactive molecules, such as thymol, amylcresol, and phenethyl resorcinol.

Key words: thiocyanation, triisopropylsilane (TIPS)-protected phenols, transition-metal-free, radical cation

Cite this article

Guodong Ju, Guangyu Zhou, Yingsheng Zhao. Transition-Metal-Free Regioselective Thiocyanation of Triisopropylsilane (TIPS)-Protected Phenols[J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1327-1336.

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Fig. & Tab. 6

Figure 1. Arylthiocyanate compounds as key intermediates with multiple functional groups

Entry	Oxidant	Solvent	[SCN] source	Yield/%
1	Oxone	HFIP	KSCN	92
2	Oxone	HFIP	AgSCN	NR
3	Oxone	HFIP	NH₄SCN	99
4	K₂S₂O₈	HFIP	NH₄SCN	86
5	H₂O₂	HFIP	NH₄SCN	83
6	O₂	HFIP	NH₄SCN	Trace
7	TBHP	HFIP	NH₄SCN	NR
8	Oxone	H₂O	NH₄SCN	NR
9	Oxone	DCE	NH₄SCN	NR
10	Oxone	EtOH	NH₄SCN	NR
11	Oxone	DMSO	NH₄SCN	NR
12	Oxone	DMF	NH₄SCN	NR
13	Oxone	Dioxane	NH₄SCN	NR
14	Oxone	THF	NH₄SCN	NR
15	Oxone	CH₃CN	NH₄SCN	NR
16	—	HFIP	NH₄SCN	NR

Table 1. Optimization of the reaction conditionsa

Scheme 1. Scope of thiocyanation with phenol derivatives Reaction conditions: 1 (0.2 mmol), 2 (0.3 mmol), oxone (2.0 equiv.), HFIP (1.0 mL) at room temperature for 1 h in a sealed tube, isolated yield.

Scheme 2. Late-stage C—H thiocyanation of pharmaceutically important molecules Reaction conditions: 1 (0.2 mmol), 2 (0.3 mmol), oxone (2.0 equiv.), HFIP (1.0 mL) at room temperature for 1 h in a sealed tube, isolated yield.

Scheme 3. Synthetic applications and radical clock experiments

Scheme 4. Possible mechanism of phenol thiocyanation

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三异丙基硅烷(TIPS)保护苯酚的无过渡金属催化区域选择性硫氰化反应

Transition-Metal-Free Regioselective Thiocyanation of Triisopropylsilane (TIPS)-Protected Phenols

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