2-芳甲酰基甲亚基丙二酸酯与Corey叶立德的反应

doi:10.6023/cjoc202209014

摘要/Abstract

研究了2-芳甲酰基甲亚基丙二酸酯与Corey叶立德的反应. 1.0 equiv.的三甲基碘化亚砜与2.5 equiv.氢化钠在N,N-二甲基甲酰胺(DMF)溶剂中制得的Corey叶立德, 与2-芳甲酰甲亚基丙二酸酯在－23 ℃条件下通过亲核加成/消除过程得到2-(1-芳甲酰基乙烯基)丙二酸酯; 2.2 equiv.的三甲基碘化亚砜与5.0 equiv.氢化钠在DMF溶剂中制得的Corey叶立德, 与2-芳甲酰甲亚基丙二酸酯在－23~0 ℃条件下通过亲核加成/消除/加成/环丙烷化过程得到2-(1-芳甲酰基环丙基)丙二酸酯; 1.1 equiv.的三甲基碘化亚砜与5.0 equiv.碳酸钾在DMF溶剂中制得的Corey叶立德, 与2-芳甲酰甲亚基丙二酸酯在0 ℃条件下通过亲核加成/环丙烷化过程得到2-芳甲酰基-1,1-环丙烷二羧酸酯. 这三种过程可以通过简单调节碱及其用量以及反应温度等条件得到高选择性控制.

关键词: 芳酰甲亚基丙二酸酯, Corey叶立德, 共轭加成, 环丙烷化

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

引用此文

陈文龙, 李慧敏, 杨鹏飞, 郑东程, 杨高升. 2-芳甲酰基甲亚基丙二酸酯与Corey叶立德的反应[J]. 有机化学, 2023, 43(4): 1472-1482.

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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参考文献 12

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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