Preparation of α-(Di(alkoxycarbonyl)methyl)chalcones and Their Application in the Synthesis of Multisubstituted Cyclopropanes

doi:10.6023/cjoc202408023

Abstract

The synthesis and cyclopropanation of α-(di(alkoxycarbonyl)methyl)chalcones were studied. In the presence of sodium hydride, 2-aroylmethylenemalonates reacted with arylmethyl p-tolyl sulfone to give α-(di(alkoxycarbonyl)methyl)- chalcones via a conjugate addition/elimination sequence. Under the promotion of sodium hydride, the reaction of α-(di(alkoxy- carbonyl)methyl)chalcones with trimethylsulfoxonium iodide proceeded via a conjugate addition/cyclopropanation sequence to give multisubstituted cyclopropane of 2-(1-aroyl-2-arylcyclopropyl)malonates. In a preliminary study, these cyclopropanes showed good reactivity in the cyclocondensation reactions with urotropin or 1,3,5-triphenyl-1,3,5-triazinane to provide structurally novel heterocyclic products under catalyst-free conditions.

Key words: synthesis, conjugate addition, chalcone, cyclopropanation

Cite this article

Junqiang Jiao, Gaosheng Yang. Preparation of α-(Di(alkoxycarbonyl)methyl)chalcones and Their Application in the Synthesis of Multisubstituted Cyclopropanes[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2586-2599.

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Entry	TsBn/equiv.	NaH/equiv.	Solvent	Temperature/℃	Time^b/h	Yield^c/% of 3aa
1	1.5	2.5	DMF	25	12	NR
2	1.5	2.5	DMF	40	10	66
3	1.5	2.5	DMF	60	6	84
4	1.5	2.5	DMF	80	3	67
5	1.5	2.0	DMF	60	24	58
6	1.5	3.0	DMF	60	5	62^d
7	1.5	2.5	THF	60	6	78
8	1.5	2.5	DMSO	60	12	90
9	1.1	2.5	DMSO	60	14	85

Entry	TsBn/equiv.	NaH/equiv.	Solvent	Temperature/℃	Time^b/h	Yield^c/% of 3aa
1	1.5	2.5	DMF	25	12	NR
2	1.5	2.5	DMF	40	10	66
3	1.5	2.5	DMF	60	6	84
4	1.5	2.5	DMF	80	3	67
5	1.5	2.0	DMF	60	24	58
6	1.5	3.0	DMF	60	5	62^d
7	1.5	2.5	THF	60	6	78
8	1.5	2.5	DMSO	60	12	90
9	1.1	2.5	DMSO	60	14	85

Entry	OS^＋(CH₃)₃I⁻/equiv.	NaH/equiv.	Solvent	Temperature/℃	Time^b/h	Yield^c/% of 4a	dr^d
1	2.0	3.0	DMF	40	96	78	96∶4
2	2.0	3.0	DMF	50	48	88	94∶6
3	2.0	3.0	DMF	60	37	80	87∶13
4	1.5	3.0	DMF	50	52	40	75∶25
5	2.5	3.0	DMF	50	72	45	90∶10
6	2.0	2.5	DMF	50	96	42	91∶9
7	2.0	3.5	DMF	50	30	75	80∶20
8	2.0	3.0	DMSO	50	48	82	89∶11
9	2.0	3.0	THF	50	78	63	88∶12

Entry	OS^＋(CH₃)₃I⁻/equiv.	NaH/equiv.	Solvent	Temperature/℃	Time^b/h	Yield^c/% of 4a	dr^d
1	2.0	3.0	DMF	40	96	78	96∶4
2	2.0	3.0	DMF	50	48	88	94∶6
3	2.0	3.0	DMF	60	37	80	87∶13
4	1.5	3.0	DMF	50	52	40	75∶25
5	2.5	3.0	DMF	50	72	45	90∶10
6	2.0	2.5	DMF	50	96	42	91∶9
7	2.0	3.5	DMF	50	30	75	80∶20
8	2.0	3.0	DMSO	50	48	82	89∶11
9	2.0	3.0	THF	50	78	63	88∶12

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