期刊
ACS CATALYSIS
卷 7, 期 8, 页码 5225-5233出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.7b01464
关键词
alkenes; anti-Markovnikov; biocatalysis; enzyme cascades; hydration; hydroamination; Meinwald rearrangement; whole-cell biotransformation
资金
- GlaxoSmithKline (GSK)
- Singapore Economic Development Board (EDB) through Green and Sustainable Manufacturing grants [279-000-331-592, 279-000-348-592]
- Ministry of Education of Singapore [R-279-000-477-112]
Biocatalytic anti-Markovnikov alkene hydroamination and hydration were achieved based on two concepts involving enzyme cascades: epoxidation-isomerization-amination for hydroamination and epoxidation isomerization reduction for hydration. An Escherichia coli strain coexpressing styrene monooxygenase (SMO), styrene oxide isomerase (SOI), omega-transaminase (CvTA), and alanine dehydrogenase (AIaDH) catalyzed the hydroamination of 12 aryl alkenes to give the corresponding valuable terminal amines in high conversion (many >= 86%) and exclusive anti-Markovnikov selectivity (>99:1). Another E. coli strain coexpressing SMO, SOI, and phenylacetaldehyde reductase (PAR) catalyzed the hydration of 12 aryl alkenes to the corresponding useful terminal alcohols in high conversion (many >= 80%) and very high anti-Markovnikov selectivity (>99:1). Importantly, SOI was discovered for stereoselective isomerization of a chiral epoxide to a chiral aldehyde, providing some insights on enzymatic epoxide rearrangement. Harnessing this stereoselective rearrangement, highly enantioselective anti-Markovnikov hydroamination and hydration were demonstrated to convert alpha-methylstyrene to the corresponding (S)-amine and (S)-alcohol in 84-81% conversion with 97-92% ee, respectively. The biocatalytic anti-Markovnikov hydroamination and hydration of alkenes, utilizing cheap and nontoxic chemicals (O-2, NH3, and glucose) and cells, provide an environmentally friendly, highly selective, and high yielding synthesis of terminal amines and alcohols.
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