17596-79-1Relevant articles and documents
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Jarowski,Hartung
, p. 564,566 (1943)
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Brode,Raasch
, p. 1449,1450 (1942)
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CO2-Assisted asymmetric hydrogenation of prochiral allylamines
Alridge, Christopher J.,De Winter, Tamara M.,Ho, Jaddie,Jessop, Philip G.
, p. 6755 - 6761 (2022/03/31)
A new methodology for the asymmetric hydrogenation of allylamines takes advantage of a reversible reaction between amines and carbon dioxide (CO2) to suppress unwanted side reactions. The effects of various parameters (pressure, time, solvent, and base additives) on the enantioselectivity and conversion of the reaction were studied. The homogeneously-catalyzed asymmetric hydrogenation of 2-arylprop- 2-en-1-amine resulted in complete conversion and up to 82% enantiomeric excess (ee). Added base, if chosen carefully, improves the enantioselectivity and chemoselectivity of the overall reaction.
Enantioselective Synthesis of β-Methyl Amines via Iridium-Catalyzed Asymmetric Hydrogenation of N-Sulfonyl Allyl Amines
Cabré, Albert,Verdaguer, Xavier,Riera, Antoni
, p. 4196 - 4200 (2019/08/16)
The iridium-catalyzed asymmetric hydrogenation of several N-sulfonyl allyl amines is reported. All substrates can be easily obtained by the Ir-catalyzed isomerization of N-tosylaziridines reported previously. The commercially available threonine-derived phosphinite (UbaPHOX) iridium complex has been found to be the best catalyst for this catalytic application, affording β-methyl amines with good to excellent ee values (up to 94%). The synthetic potential of this novel methodology was demonstrated by the formal synthesis of Lorcaserin and LY-404187. (Figure presented.).
Biocatalytic Formal Anti-Markovnikov Hydroamination and Hydration of Aryl Alkenes
Wu, Shuke,Liu, Ji,Li, Zhi
, p. 5225 - 5233 (2017/08/17)
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), ω-transaminase (CvTA), and alanine dehydrogenase (AlaDH) 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 α-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 (O2, NH3, and glucose) and cells, provide an environmentally friendly, highly selective, and high-yielding synthesis of terminal amines and alcohols.