Design and Synthesis of Peptide-Based Salen-Co(II) Complexes, and Studies on Their Catalytic Reactivity in Alkene Hydrohydrazination

doi:10.6023/cjoc202504005

Abstract

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

Cite this article

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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[1]	(a) Davie E. A. C.; Mennen S. M.; Xu Y.; Miller S. J. Chem. Rev. 2007, 107, 5759. doi: 10.1021/cr068377w
	(b) Akagawa K.; Kudo K. Acc. Chem. Res. 2017, 50, 2429. doi: 10.1021/acs.accounts.7b00211
[2]	(a) Oku J.-I.; Inoue S. J. Chem. Soc., Chem. Commun. 1981, 229.
	(b) Oku J.-I.; Ito N.; Inoue S. Makromol. Chem. 1979, 180, 1089. doi: 10.1002/macp.02.v180:4
	(c) Juliá S.; Masana J.; Vega J. C. Angew. Chem., Int. Ed. 1980, 19, 929. doi: 10.1002/anie.v19:11
[3]	(a) Metrano A. J.; Chinn A. J.; Shugrue C. R.; Stone E. A.; Kim B.; Miller S. J. Chem. Rev. 2020, 120, 11479. doi: 10.1021/acs.chemrev.0c00523
	(b) Khettar I.; Araszczuk A. M.; Schettini R. Catalysts 2023, 13, 244. doi: 10.3390/catal13020244
	(c) Fang S.; Liu Z.; Wang T. Angew. Chem., Int. Ed. 2023, 62, e202307258. doi: 10.1002/anie.v62.47
	(d) Metrano A. J.; Miller S. J. Acc. Chem. Res. 2019, 52, 199. doi: 10.1021/acs.accounts.8b00473
[4]	(a) Degrado S. J.; Mizutani H.; Hoveyda A. H. J. Am. Chem. Soc. 2001, 123, 755. pmid: 11456598
	(b) Brown M. K.; Degrado S. J.; Hoveyda A. H. Angew. Chem., Int. Ed. 2005, 44, 5306. doi: 10.1002/anie.v44:33 pmid: 11456598
	(c) Gilbertson S. R.; Chen G.; McLoughlin M. J. Am. Chem. Soc. 1994, 116, 4481. doi: 10.1021/ja00089a049 pmid: 11456598
[5]	(a) Gilbertson S. R.; Collibee S. E.; Agarkov A. J. Am. Chem. Soc. 2000, 122, 6522. doi: 10.1021/ja992306f pmid: 17206835
	(b) Christensen C. A.; Meldal M. J. Comb. Chem. 2007, 9, 79. pmid: 17206835
[6]	(a) Laungani A. C.; Breit B. Chem. Commun. 2008, 844. pmid: 22777868
	(b) Laungani A. C.; Slattery J. M.; Krossing I.; Breit B. Chem.- Eur. J. 2008, 14, 4488. doi: 10.1002/chem.v14:15 pmid: 22777868
	(c) Kokan Z.; Kirin S. I. RSC Adv. 2012, 2, 5729. doi: 10.1039/c2ra20598j pmid: 22777868
	(d) Popp B. V.; Ball Z. T. J. Am. Chem. Soc. 2010, 132, 6660. doi: 10.1021/ja101456c pmid: 22777868
	(e) Sambasivan R.; Ball Z. T. J. Am. Chem. Soc. 2010, 132, 9289. doi: 10.1021/ja103747h pmid: 22777868
	(f) Sambasivan R.; Ball Z. T. Org. Biomol. Chem. 2012, 10, 8203. doi: 10.1039/c2ob26667a pmid: 22777868
	(g) Sambasivan R.; Ball Z. T. Angew. Chem., Int. Ed. 2012, 51, 8568. doi: 10.1002/anie.201202512 pmid: 22777868
	(h) Sambasivan R.; Zheng W.; Burya S. J.; Popp B. V.; Turro C.; Clementi C.; Ball Z. T. Chem. Sci. 2014, 5, 1401. doi: 10.1039/C3SC53354A pmid: 22777868
[7]	(a) Coquière D.; Bos J.; Beld J.; Roelfes G. Angew. Chem., Int. Ed. 2009, 48, 5159. doi: 10.1002/anie.200901134 pmid: 29116792
	(b) Zheng L.; Marcozzi A.; Gerasimov J. Y.; Herrmann A. Angew. Chem., Int. Ed. 2014, 53, 7599. doi: 10.1002/anie.v53.29 pmid: 29116792
	(c) Pellegrino S.; Facchetti G.; Contini A.; Gelmi M. L.; Erba E.; Gandolfi R.; Rimoldi I. RSC Adv. 2016, 6, 71529. doi: 10.1039/C6RA16255J pmid: 29116792
	(d) Kwon Y.; Chinn A. J.; Kim B.; Miller S. J. Angew. Chem., Int. Ed. 2018, 57, 6251. doi: 10.1002/anie.v57.21 pmid: 29116792
	(e) Chinn A. J.; Kim B.; Kwon Y.; Miller S. J. J. Am. Chem. Soc. 2017, 139, 18107. doi: 10.1021/jacs.7b11197 pmid: 29116792
	(f) Kim B.; Chinn A. J.; Fandrick D. R.; Senanayake C. H.; Singer R. A.; Miller S. J. J. Am. Chem. Soc. 2016, 138, 7939. doi: 10.1021/jacs.6b03444 pmid: 29116792
[8]	Cussó O.; Giuliano M. W.; Ribas X.; Miller S. J.; Costas M. Chem. Sci. 2017, 8, 3660. doi: 10.1039/C7SC00099E
[9]	(a) Hapke M.; Hilt G. Cobalt Catalysis in Organic Synthesis: Methods and Reactions, Wiley-VCH Verlag GmbH & Co. KGaA, 2019.
	(b) Tohidi M. M.; Paymard B.; Vasquez-García S. R.; Fernández- Quiroz D. Tetrahedron 2023, 136, 133352. doi: 10.1016/j.tet.2023.133352
	(c) Michiyuki T.; Komeyama K. Asian J. Org. Chem. 2020, 9, 343. doi: 10.1002/ajoc.201900625
[10]	(a) Randaccio L.; Geremia S.; Demitri N.; Wuerges J. Molecules 2010, 15, 3228. doi: 10.3390/molecules15053228 pmid: 20657474
	(b) Genchi G.; Lauria G.; Catalano A.; Carocci A.; Sinicropi M. S. Biology 2023, 12, 1335. doi: 10.3390/biology12101335 pmid: 20657474
	(c) Giedyk M.; Goliszewska K.; Gryko D. Chem. Soc. Rev. 2015, 44, 3391. doi: 10.1039/C5CS00165J pmid: 20657474
[11]	(a) Li N.; Liu X.; Zhang Y.; Liu S.; Wang X.; Chang T.; Zhu Z.; Qin S.; Hao Y. Mol. Catal. 2023, 549, 113479.
	(b) Middya P.; Saha A.; Chattopadhyay S. Inorg. Chim. Acta 2023, 545, 121246. doi: 10.1016/j.ica.2022.121246
	(c) Schulz E. Chem. Rec. 2021, 21, 427. doi: 10.1002/tcr.v21.2
	(d) Shaw S.; White J. D. Chem. Rev. 2019, 119, 9381. doi: 10.1021/acs.chemrev.9b00074
[12]	Ortiz B.; Park S.-M. Bull. Korean Chem. Soc. 2000, 21, 405.
[13]	(a) Guo J.; Cheng Z.; Chen J.; Chen X.; Lu Z. Acc. Chem. Res. 2021, 54, 2701. doi: 10.1021/acs.accounts.1c00212 pmid: 27461578
	(b) Chen J.; Guo J.; Lu Z. Chin. J. Chem. 2018, 36, 1075. doi: 10.1002/cjoc.v36.11 pmid: 27461578
	(c) Crossley S. W.; Obradors C.; Martinez R. M.; Shenvi R. A. Chem. Rev. 2016, 116, 8912. doi: 10.1021/acs.chemrev.6b00334 pmid: 27461578
	(d) Shen X.; Chen X.; Chen J.; Sun Y.; Cheng Z.; Lu Z. Nat. Commun. 2020, 11, 783. doi: 10.1038/s41467-020-14459-x pmid: 27461578
[14]	(a) Waser J.; Carreira E. M. J. Am. Chem. Soc. 2004, 126, 5676. doi: 10.1021/ja048698u
	(b) Waser J.; Gaspar B.; Nambu H.; Carreira E. M. J. Am. Chem. Soc. 2006, 128, 11693. doi: 10.1021/ja062355+
[15]	Waser J.; Carreira E. M. Angew. Chem., nt. Ed. 2004, 43, 4099.

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

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