Design and Synthesis of Pyridine and 1,3,5-Triazine PNP Pincer Ligands and Their Application in Cobalt Catalyzed Semihydrogenation of Terminal Alkynes

doi:10.6023/cjoc202102050

Abstract

Two types of novel PNP pincer ligands were designed and synthesized. One had a pyridine core and the other had a 1,3,5-triazine. Evaluation of these ligands in cobalt catalyzed semihydrogenation by silane of terminal alkyne N-(but-3- yn-1-yl)-4-methylbenzenesulfonamide (8a) was carried out, in which both had significant effects on the reaction rate and selectivity. Ethyl 2,6-bis((S)-2-((diphenylphosphanyl)methyl)pyrrolidin-1-yl)nicotinate (L5b), which had pyridine skeleton with electron-withdrawing substituent, promoted the migratory semihydrogenation of 8a giving E-2-alkene predominatly. Further screening of metal catalysts, solvents and reducing agents revealed that the optimal reaction condition was CoCl₂/L5b/ SiH(OMe)₃/trifluoroacetic acid (THF) for E-2-alkene product. More terminal alkynes 8b~8i were tested under the optimal reaction condition to afford E-2-alkene mainly. In brief, using ligand L5b, a method of migratory semihydrogenation of terminal alkynes was developed.

Key words: PNP pincer ligand, pyridine, 1,3,5-triazine, cobalt catalysis, terminal alkyne, migratory semihydrogenation, E-2-alkene

Cite this article

Yinyin Wang, Xiaowan Lin, Piao Zhang, Meihua Shen, Huadong Xu, Defeng Xu. Design and Synthesis of Pyridine and 1,3,5-Triazine PNP Pincer Ligands and Their Application in Cobalt Catalyzed Semihydrogenation of Terminal Alkynes[J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3312-3320.

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Entry	L	Time^b/h	Ratio of products of 9a/10a/E-11a/Z-11a^c	Yield^d/%	Conversion^f/%
1	—	17	6/94/—/—	12	41
2	L5b	2	3/4/80/13	85	100
3	L5c	3.5	9/5/75/11	68	100
4	L5e	5	10/83/3/4	64	100
5	L6a	56	3/97/—/—	25	51
6	L6b	56	12/87/1/—	71	96
7	L7	1	69/29/1/1	49	100
8	L8	5	62/30/6/2	40	100
9^e	L9	56	—/—/—/—	—	0
10	L2a	56	5/95/—/—	52	70
11^e	L10	56	—/—/—/—	—	0
12	dppbz	56	22/76/1/1	15	53
13	dppp	17	95/—/4/1	25	100
14	dppf	4	21/3/67/9	38	100

Entry	L	Time^b/h	Ratio of products of 9a/10a/E-11a/Z-11a^c	Yield^d/%	Conversion^f/%
1	—	17	6/94/—/—	12	41
2	L5b	2	3/4/80/13	85	100
3	L5c	3.5	9/5/75/11	68	100
4	L5e	5	10/83/3/4	64	100
5	L6a	56	3/97/—/—	25	51
6	L6b	56	12/87/1/—	71	96
7	L7	1	69/29/1/1	49	100
8	L8	5	62/30/6/2	40	100
9^e	L9	56	—/—/—/—	—	0
10	L2a	56	5/95/—/—	52	70
11^e	L10	56	—/—/—/—	—	0
12	dppbz	56	22/76/1/1	15	53
13	dppp	17	95/—/4/1	25	100
14	dppf	4	21/3/67/9	38	100

Entry	Substrate	Time^b/h	Major product	9/10/E-11/Z-11^c	Yield^d/%
1		2		3/6/78/13	86
2		67		3/5/73/19	68
3		124		2/17/46/35	73
4		66		3/3/76/18	75
Entry	Substrate	Time^b/h	Major products	9/10/E-11/Z-11^c	Yield^d/
5		46		2/2/72/24	72
6		19		2/4/62/32	71
7		7		4/5/46/45	84
8		102		6/1/71/22	61
9		41		9/1/90 ^e	76

Entry	Substrate	Time^b/h	Major product	9/10/E-11/Z-11^c	Yield^d/%
1		2		3/6/78/13	86
2		67		3/5/73/19	68
3		124		2/17/46/35	73
4		66		3/3/76/18	75
Entry	Substrate	Time^b/h	Major products	9/10/E-11/Z-11^c	Yield^d/
5		46		2/2/72/24	72
6		19		2/4/62/32	71
7		7		4/5/46/45	84
8		102		6/1/71/22	61
9		41		9/1/90 ^e	76

基于吡啶和1,3,5-三嗪的PNP钳状配体的设计合成以及在钴催化的末端炔烃半氢化反应中的应用