Reaction of 2-Aroylmethylenemalonates with Corey Ylide

doi:10.6023/cjoc202209014

Abstract

The reactions of 2-aroylmethylenemalonates with Corey ylide were studied. Corey ylide, prepared in-situ from 1.0 equiv. of trimethylsulfoxonium iodide and 2.5 equiv. of sodium hydride in N,N-dimethylformamide (DMF), reacted with 2-aroylmethylenemalonates at －23 ℃ via a conjugate addition/elimination sequence to give 2-(1-aroylvinyl)malonates. Corey ylide, prepared in-situ from 2.2 equiv of trimethylsulfoxonium iodide and 5.0 equiv. of sodium hydride in DMF, reacted with 2-aroylmethylenemalonates at －23 to 0 ℃ by a conjugate addition/elimination/conjugate addition/cyclopropanation sequence to give 2-(1-aroylcyclopropyl)malonates. Corey ylide, prepared in-situ from 1.1 equiv. of trimethylsulfoxonium iodide and 5.0 equiv. of potassium carbonate in DMF, reacted with 2-aroylmethylenemalonates at 0 ℃ via a conjugate addition/cyclopropanation sequence to give 2-aroyl-1,1-cyclopropanedicarboxylates. These three processes can be controlled with high chemoselectivity by simply adjusting the base, the reagent ratios and the reaction temperature.

Key words: aroylmethylidene malonate, Corey ylide, conjugate addition, cyclopropanation

Cite this article

Wenlong Chen, Huimin Li, Pengfei Yang, Dongcheng Zheng, Gaosheng Yang. Reaction of 2-Aroylmethylenemalonates with Corey Ylide[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1472-1482.

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Entry	OS^＋Me₃I^-/equiv.	Base/equiv.	Solvent	T₁/T₂/℃	Time/h	Product/(yield^b/%)	Selectivity^c of 2a∶3a∶4a
1	1.2	NaH/2.5	DMF	0/0~25	10 min	2a/60	63∶37∶0
2	1.0	NaH/2.5	DMF	0/0	25 min	2a/73	80∶20∶0
3	1.0	NaH/2.5	DMF	0/－23	1.0	2a/84	91∶9∶0
4	1.0	NaH/2.5	DMF	0/－23	4.0	2a/25	29∶10∶61
5	2.0	NaH/2.0	DMF	0/0~25	1.0 (0 ℃)＋19.0	3a/45	—
6	2.2	NaH/3.5	DMF	0/－23~0	1.0 (－23 ℃)＋8.0	3a/87	9∶91∶0
7	2.2	NaH/5.0	DMF	0/－23~0	1.0 (－23 ℃)＋6.0	3a/93	0∶100∶0
8	2.2	NaH/5.0	DMF	0/0	6.0	3a/85	0∶93∶7
9	2.2	NaH/5.0	CH₂Cl₂	0/－23~0	1.0 (－23 ℃)＋9.0	4a/13	0∶0∶100
10	1.0	K₂CO₃/1.1	DMF	25/25	22.0	4a/80	0∶0∶100
11	1.1	K₂CO₃/2.5	DMF	25/0	4.0	4a/93	0∶0∶100

Entry	OS^＋Me₃I^-/equiv.	Base/equiv.	Solvent	T₁/T₂/℃	Time/h	Product/(yield^b/%)	Selectivity^c of 2a∶3a∶4a
1	1.2	NaH/2.5	DMF	0/0~25	10 min	2a/60	63∶37∶0
2	1.0	NaH/2.5	DMF	0/0	25 min	2a/73	80∶20∶0
3	1.0	NaH/2.5	DMF	0/－23	1.0	2a/84	91∶9∶0
4	1.0	NaH/2.5	DMF	0/－23	4.0	2a/25	29∶10∶61
5	2.0	NaH/2.0	DMF	0/0~25	1.0 (0 ℃)＋19.0	3a/45	—
6	2.2	NaH/3.5	DMF	0/－23~0	1.0 (－23 ℃)＋8.0	3a/87	9∶91∶0
7	2.2	NaH/5.0	DMF	0/－23~0	1.0 (－23 ℃)＋6.0	3a/93	0∶100∶0
8	2.2	NaH/5.0	DMF	0/0	6.0	3a/85	0∶93∶7
9	2.2	NaH/5.0	CH₂Cl₂	0/－23~0	1.0 (－23 ℃)＋9.0	4a/13	0∶0∶100
10	1.0	K₂CO₃/1.1	DMF	25/25	22.0	4a/80	0∶0∶100
11	1.1	K₂CO₃/2.5	DMF	25/0	4.0	4a/93	0∶0∶100

Entry	1	Ar	R	Time/h	Product	Yield^b/%
1	1a	Ph	Et	1.0	2a	84
2	1b	4-MeC₆H₄	Et	2.5	2b	79
3	1c	4-MeOC₆H₄	Et	2.5	2c	84
4	1d	3-MeOC₆H₄	Et	2.5	2d	86
5	1e	2-MeOC₆H₄	Et	2.0	2e	72
6^c	1f	4-BrC₆H₄	Et	27 min	2f	80
7^c	1g	4-ClC₆H₄	Et	20 min	2g	81
8^c	1h	4-FC₆H₄	Et	25 min	2h	60
9^c	1i	4-NO₂C₆H₄	Et	15 min	2i	61
10^c	1j	3-NO₂C₆H₄	Et	15 min	2j	60
11^c	1k	2-NO₂C₆H₄	Et	15 min	2k	64
12^c	1l	4-CF₃C₆H₄	Et	17 min	2l	74
13	1m	Ph	Me	1.0	2m	76
14^c	1p	Me	Me	5 min	2p	70

Entry	1	Ar	R	Time/h	Product	Yield^b/%
1	1a	Ph	Et	1.0	2a	84
2	1b	4-MeC₆H₄	Et	2.5	2b	79
3	1c	4-MeOC₆H₄	Et	2.5	2c	84
4	1d	3-MeOC₆H₄	Et	2.5	2d	86
5	1e	2-MeOC₆H₄	Et	2.0	2e	72
6^c	1f	4-BrC₆H₄	Et	27 min	2f	80
7^c	1g	4-ClC₆H₄	Et	20 min	2g	81
8^c	1h	4-FC₆H₄	Et	25 min	2h	60
9^c	1i	4-NO₂C₆H₄	Et	15 min	2i	61
10^c	1j	3-NO₂C₆H₄	Et	15 min	2j	60
11^c	1k	2-NO₂C₆H₄	Et	15 min	2k	64
12^c	1l	4-CF₃C₆H₄	Et	17 min	2l	74
13	1m	Ph	Me	1.0	2m	76
14^c	1p	Me	Me	5 min	2p	70

Entry	1	Ar	R	Time/h	Product	Yield^b/%
1	1a	Ph	Et	1.0 (－23 ℃)＋6 (0 ℃)	3a	93
2	1b	4-MeC₆H₄	Et	1.1 (－23 ℃)＋7 (0 ℃)	3b	90
3	1c	4-MeOC₆H₄	Et	2.0 (－23 ℃)＋12 (0 ℃)	3c	93
4	1d	3-MeOC₆H₄	Et	2.3 (－23 ℃)＋14 (0 ℃)	3d	89
5	1e	2-MeOC₆H₄	Et	1.4 (－23 ℃)＋8.5 (0 ℃)	3e	85
6	1f	4-BrC₆H₄	Et	40 min (－23 ℃)＋4.5 (0 ℃)	3f	91
7	1g	4-ClC₆H₄	Et	40 min (－23 ℃)＋4.5 (0 ℃)	3g	89
8	1h	4-FC₆H₄	Et	30 min (－23 ℃)＋3.5 (0 ℃)	3h	92
9	1i	4-NO₂C₆H₄	Et	1.1 (－23 ℃)＋7 (0 ℃)	3i'	35
10	1j	3-NO₂C₆H₄	Et	5 min (－23 ℃)＋1 (0 ℃)	3j	73
11	1k	2-NO₂C₆H₄	Et	5 min (－23 ℃)＋35 min (0 ℃)	3k	82
12	1l	4-CF₃C₆H₄	Et	10 min (－23 ℃)＋1.5 (0 ℃)	3l	60
13^c	1m	Ph	Me	1.0 (－23 ℃)＋6 (0 ℃)	3m	81 (X-ray)
14	1p	Me	Me	5 min (－23 ℃)＋40 min (0 ℃)	3p	46

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