- The asymmetric synthesis of amines via nickel-catalyzed enantioconvergent substitution reactions
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Chiral dialkyl carbinamines are important in fields such as organic chemistry, pharmaceutical chemistry, and biochemistry, serving for example as bioactive molecules, chiral ligands, and chiral catalysts. Unfortunately, most catalytic asymmetric methods for synthesizing dialkyl carbinamines do not provide general access to amines wherein the two alkyl groups are of similar size (e.g., CH2R versus CH2R1). Herein, we report two mild methods for the catalytic enantioconvergent synthesis of protected dialkyl carbinamines, both of which use a chiral nickel catalyst to couple an alkylzinc reagent (1.1-1.2 equiv) with a racemic partner, specifically, an α-phthalimido alkyl chloride or an N-hydroxyphthalimide (NHP) ester of a protected α-amino acid. The methods are versatile, providing dialkyl carbinamine derivatives that bear an array of functional groups. For couplings of NHP esters, we further describe a one-pot variant wherein the NHP ester is generated in situ, allowing the generation of enantioenriched protected dialkyl carbinamines in one step from commercially available amino acid derivatives; we demonstrate the utility of this method by applying it to the efficient catalytic enantioselective synthesis of a range of interesting target molecules.
- Yang, Ze-Peng,Freas, Dylan J.,Fu, Gregory C.
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p. 2930 - 2937
(2021/03/01)
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- Enantioselective organocatalytic reductive amination of aliphatic ketones by benzothiazoline as hydrogen donor
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The chiral phosphoric acid-catalyzed enantioselective reductive amination of aliphatic ketones with aromatic amines was successfully achieved by the use of benzothiazoline as the hydrogen donor. Corresponding chiral aliphatic amines were obtained with exc
- Saito, Kodai,Akiyama, Takahiko
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supporting information; experimental part
p. 4573 - 4575
(2012/06/15)
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- Switching from (R)- to (S)-selective chemoenzymatic DKR of amines involving sulfanyl radical-mediated racemization
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Chemoenzymatic dynamic kinetic resolution (DKR) of amines involving sulfanyl radical-induced racemization happened to be the very first switchable DKR process allowing the synthesis of either (R)- or (S)-amides, in good yield and high enantiomeric excess,
- El Blidi, Lahssen,Vanthuyne, Nicolas,Siri, Didier,Gastaldi, Stephane,Bertrand, Michele P.,Gil, Gerard
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supporting information; experimental part
p. 4165 - 4168
(2010/11/02)
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- N-Acyl glycinates as acyl donors in serine protease-catalyzed kinetic resolution of amines. Improvement of selectivity and reaction rate
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Enzymatic kinetic resolution of aliphatic and benzylic amines leading to (S)-amides was achieved by using alkaline protease as the catalyst and N-octanoyl glycine trifluoroethyl ester as the acyl donor; enantioselectivity ranged between 4 to 244, while reaction times were dramatically shortened and ranged between 15 min to 6 h. The 2008 Royal Society of Chemistry.
- Nechab, Malek,El Blidi, Lahssen,Vanthuyne, Nicolas,Gastaldi, Stephane,Bertrand, Michele P.,Gil, Gerard
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supporting information; experimental part
p. 3917 - 3920
(2009/06/28)
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