A Practical Synthesis of Enantiomerically Pure <i>N</i>-Benzyl-α-methyl Benzylamine

Metal-metal singly-bonded diruthenium complexes, bridged by naphthyridine-functionalized N-heterocyclic carbene (NHC) ligands featuring a hydroxy appendage on the naphthyridine unit, are obtained in a single-pot reaction of [Ru2(CH3COO)2(CO)4] with 1-benzyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide (BIN⋅HBr) or 1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide (PIN⋅HBr), TlBF4, and substituted benzaldehyde containing an electron-withdrawing group. The modified NHC-naphthyridine-hydroxy ligand spans the diruthenium unit in which the NHC carbon and hydroxy oxygen occupy the axial sites. All the synthesized compounds catalyze acceptorless dehydrogenation of alcohols to the corresponding aldehydes in the presence of a catalytic amount of weak base 1,4-diazabicyclo[2.2.2]octane (DABCO). Further, acceptorless dehydrogenative coupling (ADHC) of the alcohol with amines affords the corresponding imine as the sole product. The substrate scope is examined with 1 (BIN, p-nitrobenzaldehyde). A similar complex [Ru2(CO)4(CH3COO)(3-PhBIN)][Br], that is devoid of a hydroxy arm, is significantly less effective for the same reaction. Neutral complex 1 a, obtained by deprotonation of the hydroxy arm in 1, is found to be active for the ADHC of alcohols and amines under base-free conditions. A combination of control experiments, deuterium labeling, kinetic Hammett studies, and DFT calculations support metal-hydroxyl/hydroxide and metal-metal cooperation for alcohol activation and dehydrogenation. The bridging acetate plays a crucial role in allowing β-hydride elimination to occur. The ligand architecture on the diruthenium core causes rapid aldehyde extrusion from the metal coordination sphere, which is responsible for exclusive imine formation.

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Metal–Ligand Cooperation on a Diruthenium Platform: Selective Imine Formation through Acceptorless Dehydrogenative Coupling of Alcohols with Amines

Saha

Rahaman

Daw

et al. 2014

Chemistry A European J

105

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Are there concentration effects in enantioselective deprotonation of cyclic ketones?

Majewski¹,

Wu²

2002

Tetrahedron

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A Practical Synthesis of Enantiomerically Pure N-Benzyl-α-methyl Benzylamine

Abstract: Optically pure (R)- and (S)-N-benzyl-α-methyl benzylamine have been prepared on pilot plant scale from benzaldehyde and α-phenyl-ethylamine via palladium-catalyzed hydrogenation of the intermediate (R)-benzylidene-(1-phenylethyl)amine.

Cited by 2 publications

References 8 publications

Metal–Ligand Cooperation on a Diruthenium Platform: Selective Imine Formation through Acceptorless Dehydrogenative Coupling of Alcohols with Amines

Metal–Ligand Cooperation on a Diruthenium Platform: Selective Imine Formation through Acceptorless Dehydrogenative Coupling of Alcohols with Amines

Are there concentration effects in enantioselective deprotonation of cyclic ketones?

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