Carbonyl Cobalt-Catalyzed Cyclotrimerization of Terminal Alkynes in Supercritical Carbon Dioxide

doi:10.6023/cjoc201904021

Abstract

Atom-efficient [2+2+2] cycloaddition reaction of alkynes in green solvent supercritical carbon dioxide (ScCO₂) is an environmentally friendly reaction process that conforms to the principles of green chemistry. Cyclotrimerization of terminal alkynes catalyzed by Co₂(CO)₈ in pure ScCO₂ has been studied to obtain 1,2,4-trisubstituted benzene derivatives with excellent selectivity. The reaction conditions for the cyclotrimerization were optimized, such as concentration of catalyst, CO₂ pressure, reaction temperature and time. The solubility and phase behavior of the reaction materials and catalysts in ScCO₂ medium were discussed, and the mechanism of Co₂(CO)₈ catalyzed cyclotrimerization of terminal alkynes was assumed. The reaction substrate was extended from C≡C (alkyne) to C≡N (nitrile), and the alkyne-nitrile cycloaddition reaction in ScCO₂ was preliminary explored. Our optimized catalytic system for the cyclotrimerization of terminal alkynes exhibited wide substrate scope and high product selectivity, in which no organic co-solvent or additives were added. It provided a green synthetic method for 1,2,4-trisubstituted benzenes.

Key words: supercritical carbon dioxide, terminal alkyne, cyclotrimerization reaction, carbonyl cobalt catalyst, alkyne-nitrile cycloaddition reaction

Cite this article

Wang, Yaqi, Yin, Qiang, Guo, Dun, Han, Limin, Sun, Qi, Hong, Hailong, Suo, Quanling, Suo. Quanling. Carbonyl Cobalt-Catalyzed Cyclotrimerization of Terminal Alkynes in Supercritical Carbon Dioxide[J]. Chinese Journal of Organic Chemistry, 2019, 39(10): 2898-2905.

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Entry	Alkyne	Product	Yield^a/%
Entry	Alkyne	Product	a	a'
1		1a	62	Trace
2		2a	52	Trace
3		3a	58	Trace
4		4a	40	Trace
5^b		5a	67	Trace
6		6a	44	—
7		7a	53	—
8		8a	57	—

Entry	Alkyne	Product	Yield^a/%
Entry	Alkyne	Product	a	a'
1		1a	62	Trace
2		2a	52	Trace
3		3a	58	Trace
4		4a	40	Trace
5^b		5a	67	Trace
6		6a	44	—
7		7a	53	—
8		8a	57	—

Entry	Alkyne^b	Catalyst	Solvent	Yield^c/%
Entry	Alkyne^b	Catalyst	Solvent	b	b'	a
1^d	1	Co₂(CO)₈	ScCO₂	—	—	29
2^d	7	Co₂(CO)₈	ScCO₂	—	—	36
3^e	7	CpCo(CO)₂	ScCO₂	30	10	17
4^e	7	Co₂(CO)₆(μ₂-η²-FcC≡CH)	ScCO₂	8	2	51
5^f	7	Co₂(CO)₈	Toluene	—	—	55
6^f	7	CpCo(CO)₂	Toluene	51	22	10
7^f	7	Co₂(CO)₆(μ₂-η²-FcC≡CH)	Toluene	9	4	38

Entry	Alkyne^b	Catalyst	Solvent	Yield^c/%
Entry	Alkyne^b	Catalyst	Solvent	b	b'	a
1^d	1	Co₂(CO)₈	ScCO₂	—	—	29
2^d	7	Co₂(CO)₈	ScCO₂	—	—	36
3^e	7	CpCo(CO)₂	ScCO₂	30	10	17
4^e	7	Co₂(CO)₆(μ₂-η²-FcC≡CH)	ScCO₂	8	2	51
5^f	7	Co₂(CO)₈	Toluene	—	—	55
6^f	7	CpCo(CO)₂	Toluene	51	22	10
7^f	7	Co₂(CO)₆(μ₂-η²-FcC≡CH)	Toluene	9	4	38

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