基于多肽的Salen-Co(II)配合物的设计、合成及其在烯烃氢肼化反应中的催化活性研究

doi:10.6023/cjoc202504005

摘要/Abstract

使用三个Salen骨架SA1~SA3和四条寡肽P1~P4制备了9个多肽修饰的Salen-Co(II)配合物. 采用肉桂醇的氢肼化反应来评价这些金属配合物的催化活性. 虽然基于骨架SA1的催化剂缺少催化性能, 但是它们的母体配合物¹SalenCo和基于骨架SA2和SA3的多肽修饰的金属配合物则表现出优秀的催化活性. 这些结果表明多肽对Salen钴金属配合物的催化活性的影响不容忽视, 并且在低温条件下更明显.

关键词: 多肽, Salen配体, 多肽修饰的金属配合物, 烯烃的氢肼化

Nine peptide-modified Salen-Co(II) complexes based on three Salen ligand frameworks SA1~SA3 and four oligopeptides P1~P4 have been prepared. Their catalytic activities were examined through a model hydrohydrazination of cinnamic alcohol with azodicarboxylate. While peptide-modified Salen-Co(II) complexes derived from SA1 are ineffective, its parent ¹SalenCo and those based on SA2 and SA3 are excellent catalyst for this reaction. These results demonstrate that peptide ligands significantly modulate the catalytic activity of SalenCo(II) complexes, particularly at lower temperatures, likely due to hydrogen-bonding interactions.

Key words: peptide, Salen ligand, peptide-based metal complex, hydrohydrazination of alkene

引用此文

李增峰, 李成蹊, 张飘, 汤锦梦, 朱啻凡, 胡国栋, 沈美华, 徐华栋. 基于多肽的Salen-Co(II)配合物的设计、合成及其在烯烃氢肼化反应中的催化活性研究[J]. 有机化学, 2025, 45(12): 4425-4432.

Zengfeng Li, Chengxi Li, Piao Zhang, Jinmeng Tang, Chifan Zhu, Guodong Hu, Meihua Shen, Hua-Dong Xu. Design and Synthesis of Peptide-Based Salen-Co(II) Complexes, and Studies on Their Catalytic Reactivity in Alkene Hydrohydrazination[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4425-4432.

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Entry	Px^zSalenCo	Temperature/℃	Time/h	Conversion^b/%	Yield^c/%	ee^d/%
1	P1¹SalenCo	30	3.0	≈5	Trace	—
2	P1²SalenCo	30	3.0	100	81	0
3	P1³SalenCo	30	3.0	100	90	0
4	P2¹SalenCo	30	3.0	≈5	Trace	—
5	P2²SalenCo	30	3.0	100	73	0
6	P2³SalenCo	30	3.0	100	62	0
7	P3²SalenCo	30	3.0	100	95	0
8	P4²SalenCo	30	3.5	100	95	0
9	P4³SalenCo	30	3.0	100	80	0
10	P1²SalenCo	15	3.0	80	66 (83)^e	—
11	P2²SalenCo	15	3.0	60	42 (70)^e	0
12	P3²SalenCo	15	3.0	40	36 (90)^e	—
13	P4²SalenCo	15	3.0	50	45 (90)^e	0
14	¹SalenCo	15	3.0	100	97	—
15	²SalenCo	15	3.0	<30	98^f	—
16	³SalenCo	15	3.0	<50	95^f	—

Entry	Px^zSalenCo	Temperature/℃	Time/h	Conversion^b/%	Yield^c/%	ee^d/%
1	P1¹SalenCo	30	3.0	≈5	Trace	—
2	P1²SalenCo	30	3.0	100	81	0
3	P1³SalenCo	30	3.0	100	90	0
4	P2¹SalenCo	30	3.0	≈5	Trace	—
5	P2²SalenCo	30	3.0	100	73	0
6	P2³SalenCo	30	3.0	100	62	0
7	P3²SalenCo	30	3.0	100	95	0
8	P4²SalenCo	30	3.5	100	95	0
9	P4³SalenCo	30	3.0	100	80	0
10	P1²SalenCo	15	3.0	80	66 (83)^e	—
11	P2²SalenCo	15	3.0	60	42 (70)^e	0
12	P3²SalenCo	15	3.0	40	36 (90)^e	—
13	P4²SalenCo	15	3.0	50	45 (90)^e	0
14	¹SalenCo	15	3.0	100	97	—
15	²SalenCo	15	3.0	<30	98^f	—
16	³SalenCo	15	3.0	<50	95^f	—

Entry	Px^zSalenCo	Time/h	Conversion^b/%	Yield^c/%
1	P1¹SalenCo	3.0	≈5	Trace
2	P1²SalenCo	3.0	100	63
3	P1³SalenCo	3.0	100	50
4	P2¹SalenCo	3.0	≈5	Trace
5	P2²SalenCo	3.0	100	31
6	P2³SalenCo	3.0	100	15
7	P3²SalenCo	3.0	100	36
8	P4²SalenCo	3.0	100	52
9	P4³SalenCo	3.0	100	47

Entry	Px^zSalenCo	Time/h	Conversion^b/%	Yield^c/%
1	P1¹SalenCo	3.0	≈5	Trace
2	P1²SalenCo	3.0	100	63
3	P1³SalenCo	3.0	100	50
4	P2¹SalenCo	3.0	≈5	Trace
5	P2²SalenCo	3.0	100	31
6	P2³SalenCo	3.0	100	15
7	P3²SalenCo	3.0	100	36
8	P4²SalenCo	3.0	100	52
9	P4³SalenCo	3.0	100	47

Entry	Px^zSalenCo	Time/h	Conversion^b/%	Yield^c/%
1	P1¹SalenCo	3.0	100	Messy
2	P1²SalenCo	3.0	100	86
3	P1³SalenCo	3.0	100	93
4	P2¹SalenCo	3.0	≈5	Trace
5	P2²SalenCo	3.0	100	96
6	P2³SalenCo	3.0	100	95
7	P3²SalenCo	3.0	100	85
8	P4²SalenCo	3.0	100	95
9	P4³SalenCo	3.0	100	99