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. 2013 Jul 5;3(7):1652-1656.
doi: 10.1021/cs400360e.

Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature (V体育官网)

Jinho Kim  1 , Shannon S Stahl
Affiliations

Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature

Jinho Kim et al. ACS Catal. .

Abstract

An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4'- t Bu2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3. 3. 1]nonan-3-one N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines VSports手机版. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction. .

Keywords: aerobic oxidation; amine oxidation; copper; nitrile; nitroxyl. V体育安卓版.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Problematic substrates for of CuI/ABNO-catalyzed amine oxidation.
Figure 2
Figure 2
Reaction time course, monitored by gas uptake (O2) and GC analysis of the organic products (nitrile and imine), showing the 1:1 relationship between O2 consumption and nitrile formed. See supporting information for details.
Figure 3
Figure 3
Isotope-effect (A) and Hammett (B) data from CuI/ABNO-catalyzed aerobic oxidation of p-methoxybenzyl-amine to p-methoxybenzonitrile.
Figure 4
Figure 4
O2-dependence kinetic data from CuI/ABNO-catalyzed aerobic oxidation of p-methoxybenzylamine to p-methoxy-benzonitrile.
Scheme 1
Scheme 1
The selectivity of Cu/nitroxyl catalyzed primary amine oxidation.
Scheme 2
Scheme 2
Simplified catalytic cycle for (tBu2bpy)CuI/-ABNO catalyzed aerobic amine oxidation.
Scheme 3
Scheme 3
Investigation of the possiblities of homocoupled imine intermediates.
Scheme 4
Scheme 4
Complementary pathways for the preparation of nitriles from 1° amines or 1° alcohols/ammonia.
Scheme 5
Scheme 5
Preliminary results of aerobic oxidative coupling of alcohols and ammonia to form nitriles.
See this image and copyright information in PMC

References

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    1. For a review of aerobic oxidation of amines, see: Schümperli MT, Hammond C, Hermans I. ACS Catal. 2012;2:1108.

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    1. For leading references to Cu/TEMPO and related catalyst systems for amine oxidation, see the following: Han B, Yang XL, Wang C, Bai YW, Pan TC, Chen X, Yu W. J Org Chem. 2012;77:1136.Hu (VSports在线直播) Z, Kerton FM. Org Biomol Chem. 2012;10:1618.Sonobe T, Oisaki K, Kanai M. Chem Sci. 2012;3:3249.Huang B, Tian H, Lin S, Xie M, Yu X, Xu Q. Tetrahedron Lett. 2013;54:2861.