One-Pot Synthesis of Tetrahydro-2H-selenopyran Derivatives from Benzalacetones, Elemental Selenium, and Sodium Borohydride

doi:10.6023/cjoc202311017

Abstract

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

Cite this article

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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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

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