Biocatalytic aminohydroxylation of styrenes for efficient synthesis of enantiopure β-amino alcohols

doi:10.1016/S1872-2067(22)64174-3

Abstract

Abstract:

A general biocatalytic process of intermolecular aminohydroxylation of styrenes with aniline has been achieved for efficient one-pot preparation of enantiopure β-amino alcohols. The reaction involves first asymmetric epoxidation of alkene substrates by a heme-dependent monooxygenase (P450) or the FAD-dependent styrene monooxygenase, followed by the aminolysis of nascent epoxide intermediates with aniline in water solution. Hybrid cluster-continuum (HCC) model calculations reveal the mechanism of the aminolysis of epoxide with aniline as well as the critical role of the water in mediating such a reaction. In addition, the combined experiments with simulations demonstrate that the chirality of amino alcohol is determined by the absolute configuration of the epoxide formed in the enzymatic reaction. In conclusion, the developed biocatalytic process provides an efficient, environmentally friendly approach for production of high value-added enantiopure β-amino alcohols, starting from cheap and readily available alkenes.

Key words: Aminohydroxylation, β-amino alcohols, Alkene monooxygenase, Aminolysis of epoxide, Chemoenzymatic reaction

Ruiwen Hu, Anjie Gong, Langxing Liao, Yan-Xin Zheng, Xin Liu, Peng Wu, Fushuai Li, Huili Yu, Jing Zhao, Long-Wu Ye, Binju Wang, Aitao Li. Biocatalytic aminohydroxylation of styrenes for efficient synthesis of enantiopure β-amino alcohols[J]. Chinese Journal of Catalysis, 2023, 44: 171-178.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64174-3

https://www.cjcatal.com/EN/Y2023/V44/I1/171

Figures/Tables 5

Fig. 1. Traditional chemical and proposed biocatalytic approaches for the production of β-amino alcohols. (a) Current process for β-amino alcohols synthesis by multistage chemical methods, including first asymmetric epoxidation with Jacobsen metal catalysts, followed by aminolysis of epoxides with an excess amine in presence of a Lewis acid or different organic solvents. (b) Proposed one-pot biocatalytic method for β-amino alcohols synthesis with an alkene monooxygenase as catalyst and the thereby generated epoxide serving as an intermediate.

Fig. 2. The asymmetric intermolecular aminohydroxylation of styrene 1a with aniline 1b to produce β-amino alcohols 1c and 1d by using P450-BM3 WT as catalyst. Reaction conditions: cell suspension in phosphate buffer (OD600 ≈ 40, pH = 8.5, 200 mmol/L), 2 mmol/L 1a and 2 mmol/L 1b, DMSO (2% v/v), 25 °C, 220 r/min; the cofactor NADPH is provided by the E. coli host cells using 25 mmol/L glucose as an energy source.

Fig. 3. Gibbs energy profile (in kcal/mol) for the addition of aniline to (S)-styrene oxide. Alongside the energy profile are shown the schematic drawings and optimized structures of key species. The optimized structures of key species involved in reactions are shown below.

Fig. 4. The P450-BM3 F87G and styrene monooxygenase styAB catalyzed intermolecular aminohydroxylation of styrene with aniline to produce the corresponding β-amino alcohols. (a) Time course of recombinant E. coli (P450-BM3 F87G) catalyzed asymmetric intermolecular aminohydroxylation of styrene with aniline for the production of (S)-1c in a one-pot two-step approach. (b) Time course of recombinant E. coli (styAB) catalyzed asymmetric intermolecular aminohydroxylation of styrene with aniline for the production of (R)-1c in a one-pot two-step approach. Reaction conditions: recombinant E. coli cells expressing P450-BM3 F87G or styAB were resuspended in phosphate buffer (pH = 8.5, 200 mmol/L) at a cell density of OD600 ≈ 40, styrene (5 mmol/L) was first added and reacted for 1 h, followed by addition of aniline (30 mmol/L) for another 23 h reaction; reactions were performed at 25 °C, 220 r/min with cofactor NADPH provided by the E. coli host cells using 25 mmol/L glucose as an energy source.

Table 1 Asymmetric intermolecular aminohydroxylation of para-styrenes 1a?4a with aniline to produce the corresponding enantiopure β-amino alcohols 1c?4c catalyzed by E. coli (P450-BM3 F87G), E. coli (P450pyrTM) or E. coli (styAB) a.

Entry	Sub.	Enzymes	Prod.	Yiled^b (%)	ee ^c (%)
1	1a	P450-BM3 F87G	(S)-1c	90	90
2	1a	styAB	(R)-1c	90	99
3	2a	P450pyrTM	(S)-2c	93	99
4	3a	P450pyrTM	(S)-3c	87	90
5	2a	styAB	(R)-2c	92	99
6	3a	styAB	(R)-3c	86	99
7	4a	styAB	(R)-4c	97	95

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