苄叉丙酮、硒粉和硼氢化钠一锅法构建四氢-2H-硒吡喃衍生物

doi:10.6023/cjoc202311017

摘要/Abstract

报道了一种以苄叉丙酮、硒粉和硼氢化钠为原料, 采用一锅法合成一系列四氢-2H-硒吡喃衍生物的新方法. 此反应通过形成6个新的化学键很好的构建一系列含硒六元环. 得到了20个含有四氢-2H-硒吡喃结构的小分子化合物, 最高产率可达91%. X单晶衍射分析表明四氢-2H-硒吡喃六元环与环己烷具有类似的空间立体结构, 呈现出稳定的椅式构象. 此反应在克量级规模下依然可以顺利进行. 可能的反应机理表明此反应为涉及双Michael加成/二硒键的断裂/Mi- chael加成/Aldol反应的多步串级反应. 此方法具有底物适应性强、不使用过度金属催化剂以及反应条件温和的特点.

关键词: 四氢-2H-硒吡喃, 环化, 硒, 一锅法, 苄叉丙酮

A reaction has been developed to synthesize a series of tetrahydro-2H-selenopyran derivatives from benzalace- tones, sodium borohydride, and elemental selenium by one-pot method. The reaction proceeds well to construct a tetrahydro-2H-selenopyran ring and six new bonds. Twenty tetrahydro-2H-selenopyran derivatives were obtained, and the yield was up to 91%. The X-ray single crystal analysis showed that this selenium-containing heterocyclic ring exists as a stable chair conformation similar to cyclohexane. The reaction works well when scaled up to the gram scale. A possible mechanism was proposed, involving hydrogenation of selenium/double Michael addition/cleavage of diselenide bond/Michael addition/Aldol reaction. This reaction is characterized by high compatibility to substrates, transition-metal free, and mild reaction conditions.

Key words: tetrahydro-2H-selenopyran, cyclization, elemental selenium, one-pot, benzalacetones

引用此文

陈栋栋, 杨旭锋. 苄叉丙酮、硒粉和硼氢化钠一锅法构建四氢-2H-硒吡喃衍生物[J]. 有机化学, 2024, 44(5): 1641-1648.

Dongdong Chen, Xufeng Yang. One-Pot Synthesis of Tetrahydro-2H-selenopyran Derivatives from Benzalacetones, Elemental Selenium, and Sodium Borohydride[J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1641-1648.

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参考文献 15

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Entry	Solvent	Time/h	T/℃	Yield^b/%
1	H₂O	6	r.t.	0
2	MeOH	6	r.t.	37
3	EtOH	6	r.t.	46
4	EtOH	12	r.t.	62
5	MeCN/H₂O (V∶V=1∶1)	12	r.t.	13
6	DMF/H₂O (V∶V=1∶1)	12	r.t.	<10
7	DMSO/H₂O (V∶V=1∶1)	12	r.t.	<10
8	MeOH/H₂O (V∶V=1∶1)	12	r.t.	79
9	EtOH/H₂O (V∶V=1∶1)	12	r.t.	88
10	EtOH/H₂O (V∶V=1∶1)	6	r.t.	59
11	EtOH/H₂O (V∶V=1∶1)	24	r.t.	75
12	EtOH/H₂O (V∶V=1∶1)	12	50	71
13	EtOH/H₂O (V∶V=1∶1)	12	0	80

Entry	Solvent	Time/h	T/℃	Yield^b/%
1	H₂O	6	r.t.	0
2	MeOH	6	r.t.	37
3	EtOH	6	r.t.	46
4	EtOH	12	r.t.	62
5	MeCN/H₂O (V∶V=1∶1)	12	r.t.	13
6	DMF/H₂O (V∶V=1∶1)	12	r.t.	<10
7	DMSO/H₂O (V∶V=1∶1)	12	r.t.	<10
8	MeOH/H₂O (V∶V=1∶1)	12	r.t.	79
9	EtOH/H₂O (V∶V=1∶1)	12	r.t.	88
10	EtOH/H₂O (V∶V=1∶1)	6	r.t.	59
11	EtOH/H₂O (V∶V=1∶1)	24	r.t.	75
12	EtOH/H₂O (V∶V=1∶1)	12	50	71
13	EtOH/H₂O (V∶V=1∶1)	12	0	80