Photoredox cobalt-catalyzed stereodivergent synthesis of 1,4-dienes

doi:10.1016/S1872-2067(24)60031-8

Abstract

Abstract:

1,4-Dienes are important scaffolds widely used in natural products and medicinal compounds. Herein, we report a highly efficient method for the straightforward synthesis of 1,4-dienes via regio- and stereoselective reductive coupling of alkynes and allenes, catalyzed by visible-light photoredox cobalt. In contrast to the conventional E-alkene products, both (Z,E)- and (E,E)-1,4-dienes were synthesized with good regio- and stereoselectivities under mild conditions. In this photoredox reaction, Hünig’s base and water were utilized as hydrogen sources instead of the commonly used Hantzsch esters. The mechanistic and density functional theory studies indicate that the reaction undergoes protolysis of a cobaltacyclopentene intermediate and photocatalytic E→Z isomerization of (E,E)-1,4-dienes to (Z,E)-1,4-dienes via an energy transfer process.

Key words: 1,4-Dienes, Cobalt catalysis, Photoredox, Reductive coupling, Alkynes, Allenes

Xing-Yu Ren, Jia-Jun Liu, Shi-Qi Zhang, Yan-Lin Li, Kun Cui, Jing Li, Zheng-Yang Gu, Ji-Bao Xia. Photoredox cobalt-catalyzed stereodivergent synthesis of 1,4-dienes[J]. Chinese Journal of Catalysis, 2024, 61: 291-300.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60031-8

https://www.cjcatal.com/EN/Y2024/V61/I6/291

Figures/Tables 6

Fig. 1. Selective synthesis of 1,4-dienes. (A) Bioactive natural products containing 1,4-diene motifs. (B) Catalytic reactions for the synthesis of 1,4-dienes. X: H or halogen group. (C) Photosensitizer-controlled stereodivergent synthesis of 1,4-dienes. HE: Hantzsch esters. (D) This work: Solvent-controlled stereodivergent synthesis of 1,4-dienes.

Table 1 Summary of the effects of reaction parameters on the reaction efficiency a.

Entry	Co catalysis	Ligand	Solvent	Yield of 3 ^b (%)	Yield of 4 ^b (%)
1	Co(acac)₂	Xantphos	MeCN	21	<2
2	CoBr₂	Xantphos	MeCN	25	<2
3	CoCl₂	Xantphos	MeCN	20	<2
4	Co(OAc)₂	Xantphos	MeCN	55	<2
5	Co(OAc)₂	DPPP	MeCN	<2	<2
6	Co(OAc)₂	DPPE	MeCN	<2	<2
7	Co(OAc)₂	Nixantphos	MeCN	67	<2
8	Co(OAc)₂	Nixantphos	THF	12	36
9	Co(OAc)₂	Nixantphos	2-MeTHF	17	45
10^c	Co(OAc)₂	Nixantphos	2-MeTHF	19	55
11	Co(OAc)₂	Nixantphos	1,4-Dioxane	<2	<2
12	Co(OAc)₂	Nixantphos	MeOH	8	<2
13^d	Co(OAc)₂	Nixantphos	MeCN	75	<2

Fig. 2. Reaction scope of 1,4-dienes. All reactions were performed with alkynes (0.2 mmol) and allenes (0.4 mmol) in MeCN (2 mL) to obtain the isolated products. The rr ratio stands for the reaction major coupling at β-position of alkynes. The stereochemistry of the product was confirmed by 1H-1H NOESY analysis of 5 and 22.

Fig. 3. Reaction scope of 1,4-dienes and transformations. (A) Examples of (E,E)-1,4-dienes. All reactions were performed with alkynes (0.2 mmol) and allenes (0.6 mmol) in 2-MeTHF (2 mL); isolated yield of product is provided. The stereochemistry of the product was confirmed by 1H-1H NOESY analysis of 33. aCrude E/Z ratio was determined by GC-MS analysis. (B) Reaction of butynoate with allene 2. (C) Scale-up of alkynes 1 and 2. (D) Hydrolysis of ester groups into acidic groups.

Fig. 4. Control experiments and mechanistic studies. (A) Control reaction without H2O. (B) Deuterium-labeling experiments using D2O. (C) Effect of ester group. (D) Visible light-induced isomerization of alkene. (E) Triplet-state energies affected by solvents. (F) DFT studies of the free energies of the key intermediates. All the calculations were performed at the M06-L/6-31G(d)/SDD (for Co)/pcm (THF or MeCN) level of theory. Free energies are expressed in kcal mol?1.

Fig. 5. Proposed reaction mechanism.

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