Synthesis of Benzochromenes via Brønsted Acid Catalyzed Annulation of Naphthol with Propargyl Alcohols

doi:10.6023/cjoc202312012

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (6): 1920-1928.DOI: 10.6023/cjoc202312012 Previous Articles Next Articles

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Brønsted酸催化萘酚与丙炔醇的环化反应合成苯并色烯

赵聘^a, 尚旭伟^b, 罗清清^b, 梁梦雨^b, 符媛^b, 张明亮^b^,^*(), 刘澜涛^a^,^b^,^*()

a 郑州大学化学学院郑州 450001
b 商丘师范学院化学化工学院河南省药物绿色合成工程研究中心河南商丘 476000

收稿日期:2023-12-13 修回日期:2024-02-23 发布日期:2024-03-12
基金资助:
国家自然科学基金(21572126); 国家自然科学基金(21901152); 河南省科技攻关(202102310003); 河南省商丘市人才支持计划领军人才(SQRC202212004)

Synthesis of Benzochromenes via Brønsted Acid Catalyzed Annulation of Naphthol with Propargyl Alcohols

Pin Zhao^a, Xuwei Shang^b, Qingqing Luo^b, Mengyu Liang^b, Yuan Fu^b, Mingliang Zhang^b,*(), Lantao Liu^a^,^b,*()

a College of Chemistry, Zhengzhou University, Zhengzhou 450001
b Henan Engineering Laboratory of Green Synthesis for Pharmaceuticals, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000

Received:2023-12-13 Revised:2024-02-23 Published:2024-03-12
Contact: * E-mail: liult05@iccas.ac.cn;moonlightzhang@163.com
Supported by:
National Natural Sciences Foundation of China(21572126); National Natural Sciences Foundation of China(21901152); Key Scientific and Technological Project of Henan Province(202102310003); Leading Talent Funding Project of Shangqiu Talent Support Plan in Henan Province(SQRC202212004)

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Abstract

Benzeochromenes, also named as naphthopyrans, are widely found in natural products, bioactive molecules and organic functional materials. A simple and efficient strategy for the synthesis of benzeochromenes with propargyl alcohols and β-naphthols under mild conditions was developed, and a series of benzeochromenes were prepared in excellent yields. This protocol has the advantages of broad scope, functional group diversity and mild conditions with H₂O as the only byproduct. Moreover, ease of operation and gram-scale preparation portend the practical application.

Key words: naphthopyran, benzeochromene, propargyl alcohols, 2-naphthol

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Pin Zhao, Xuwei Shang, Qingqing Luo, Mengyu Liang, Yuan Fu, Mingliang Zhang, Lantao Liu. Synthesis of Benzochromenes via Brønsted Acid Catalyzed Annulation of Naphthol with Propargyl Alcohols[J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1920-1928.

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Fig. & Tab. 6

Figure 1. Selected benzeochromene-containing natural products, bioactive compounds and functional molecules

Scheme 1. (a) Methods with high reaction temperature, sensitive catalyst or relatively low yields, (b) methods with less hindered 1,1-diphenylpropyn-l-ol as substrate, (c) methods with more active propargylic alcohols D, and (d) strategy in this work

Entry	Cat.	Solvent	Yield^b/%
1	(PhO)₂PO₂H	DCM	47
2	TsOH	DCM	98
3	H₃PO₄	DCM	23
4	PhCO₂H	DCM	Trace
5	AcOH	DCM	Trace
6	TsOH	EtOAc	N.d.
7	TsOH	THF	Trace
8	TsOH	CH₃CN	59
9	TsOH	Toluene	90
10^c	TsOH	DCM	79
11^d	TsOH	DCM	81
12^e	TsOH	DCM	95
13^f	TsOH	DCM	77
14^g	TsOH	DCM	84

Table 1. Optimization of reaction conditionsa

Table 2. Substrates scope propargyl alcohols with 2-naphthols a

Scheme 2. (a) Gram-scale reaction, and (b) synthetic usage of this strategy

Scheme 3. Proposed reaction pathway

References 21

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Brønsted酸催化萘酚与丙炔醇的环化反应合成苯并色烯

Synthesis of Benzochromenes via Brønsted Acid Catalyzed Annulation of Naphthol with Propargyl Alcohols

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