Palladium-catalyzed enantioselective linear allylic alkylation of vinyl benzoxazinanones: An inner-sphere mechanism

doi:10.1016/S1872-2067(20)63751-2

Abstract

Abstract:

Palladium-catalyzed asymmetric allylic alkylation (AAA) of vinyl benzoxazinanones has become an important strategy for the synthesis of chiral nitrogen-containing heterocycle compounds. However, the asymmetric synthesis of linear-selective products has rarely been reported. The simultaneous control of regio-, E/Z- and enantioselectivities constitutes a major challenge and inhibits the advancement of this chemistry. Herein, we present a palladium-catalyzed AAA of vinyl benzoxazinanones with α-thiocyanato ketones, affording various chiral thiocyanates characterized with high linear-, E- and stereoselectivities. The reaction has a broad substrate scope and the chiral thiocyanates can be transformed to useful heterocycles. Experimental and computational studies suggest an inner-sphere mechanism for AAA process, which results from the acidic and coordination effect of the nucleophilic substrates with palladium catalyst.

Key words: Pd catalysis, Asymmetric catalysis, Allylic alkylation, Vinyl benzoxazinanones, Inner-sphere mechanism

Kai Wang, Binli Wang, Xianghui Liu, Hongjun Fan, Yan Liu, Can Li. Palladium-catalyzed enantioselective linear allylic alkylation of vinyl benzoxazinanones: An inner-sphere mechanism[J]. Chinese Journal of Catalysis, 2021, 42(7): 1227-1237.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63751-2

https://www.cjcatal.com/EN/Y2021/V42/I7/1227

Figures/Tables 8

Scheme 1. The chemistry of vinyl benzoxazinanones.

Table 1 Optimization of reaction conditions a.


Entry	Ligand	Solvent	t (h)	Yield ^b (%)	ee ^c (%)
1	L1	DCM	3.0	48	85
2	L2	DCM	1.5	69	60
3	L3	DCM	1.5	57	53
4	L4	DCM	3.5	15	‒24
5	L5	DCM	12	trace	—
6	L6	DCM	12	trace	—
7	L7	DCM	12	trace	—
8	L1	THF	3.0	26	83
9	L1	MeOH	3.0	trace	—
10	L1	CHCl₃	3.0	42	84
11	L1	toluene	3.0	57	86
12	L1	CH₃CN	3.0	38	84
13	L1	DCE	3.0	50	87
14 ^d	L1	DCE	3.0	29	89
15 ^e	L1	DCE	3.0	35	80
16 ^f	L1	DCE	24	70	91

Scheme 2 Substrate scope of vinyl benzoxazinanones 1 and α-thiocyanato ketones 2. Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), Pd2(dba)3·CHCl3 (5 mol%), chiral ligand L1 (11 mol%) and K2CO3 (2.0 equiv.) in 2 mL DCE at 0 °C for 24 h, isolated yields. a 4.0 equiv. K2CO3 was employed.

Scheme 3. Control experiments.

Fig. 1. Three possible reaction models proposed for this allylic alkylation reaction. Model A: hydrogen bond direction. Model B: ion pair intermediate. Model C: α-thiocyanato ketone coordinated π-allyl Pd complex.

Fig. 2. The reaction energy profile for the Pd(0)-catalyzed allylic substitution with α-thiocyanato ketones through inner-sphere mechanism. Energies are the free energies in DCE in kcal/mol, and bond lengths are in ?. The hydrogens attached on carbon atoms was omitted for clarity.

Scheme 4. Substrate scope of α-acyl indanones. Reaction conditions: 1a (0.1 mmol or 0.05 mmol), 8 (1.5 equiv.), Pd2(dba)3·CHCl3 (5 mol%), chiral ligand L1 (11 mol%) and K2CO3 (2.0 equiv.) in DCE (1.0 mL or 0.5 mL) at 0 °C for 4 h, isolated yields.

Scheme 5. Synthetic utility.

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