Citation: He Yunqing, Teng Jinwei, Tian Chong, Borzov Maxim, Hu Qishan, Nie Wanli. Reductive Amination by One Pot Reaction of Aldehydes and Alkoxyamines Catalyzed by B(C₆F₅)₃[J]. Acta Chimica Sinica, ;2018, 76(10): 774-778. doi: 10.6023/A18070281 shu

Reductive Amination by One Pot Reaction of Aldehydes and Alkoxyamines Catalyzed by B(C₆F₅)₃

a.
Sichuan Province Key Laboratory of Natural Products and Small Molecule Synthesis, Chemical Department of Leshan Normal University, Leshan 614000, China
b.
College of Chemistry and Chemical Engineering, Sichuan University of Arts and Science, Dazhou 635000, China

Corresponding author: Nie Wanli, niewl126@126.com
Received Date: 18 July 2018
Available Online: 6 October 2018
Fund Project: Scientific Research Fund of Leshan Normal University Z1308the National Natural Science Foundation of China 21542011Project supported by the National Natural Science Foundation of China (21542011), and Scientific Research Fund of Leshan Normal University (Z1414, Z1308)Scientific Research Fund of Leshan Normal University Z1414

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Recently the research work concerning B(C₆F₅)₃ catalyzed reductive and amination of aldehydes and ketones revealed that this extremely electron-deficient borane is, actually, a rather water-tolerant catalyst. This fact considerably broadens the scope of the water/base tolerant FLP chemistry. In this project, an efficient one pot reductive amination method has been developed by reaction of aldehydes and alkoxyamines with hydrosilanes as the hydride sources and B(C₆F₅)₃ as catalyst without cleavage of the N-O bond. This protocol can be used to prepare the secondary and tertiary alkoxyamines by starting from the primary and secondary ones, respectively. A special attention has been paid to elucidate the role of water in the reductive amination. When benzaldehyde reacts with benzoxylamine, only the condensation product oxime ether could be observed. Whereas surprisingly when excess amount of water is added, the reductive amination goes successfully like the alkoxyamine hydrochloride works. The detailed NMR data has shown that a transformation of the intermediate oximes ArCH=NOR to the "ammonium borates"[ArCH=NHOR]⁺[X-B(C₆F₅)₃]^-(X=Cl, OH) can take place in the reaction system, while the latter can be converted into the well-known active intermediate "ammonium hydroborates"[ArCH=NHOR]⁺[H-B(C₆F₅)₃]^- to reduce the C=N bond under mild condition in the presence of hydrosilanes. That means the deprotonation reaction of the Lewis acid water adduct H₂O-B(C₆F₅)₃ could be a key step for the B(C₆F₅)₃ catalyzed reaction under moist condition. In this case the adduct H₂O-B(C₆F₅)₃ acts as a Brønsted acid as HCl does. Meanwhile a simulative experiment under different ratio of water has been fulfilled to prove this speculation. The C=N bond of Benzalaniline (PhCH=NPh) and Benzyloxy oxime ether (PhCH=NOCH₂Ph) could be reduced only in presence of 2 equiv. H₂O rather than equivalent. Based on this study it has shown that in the frustrated Lewis pair (FLP) chemistry, the Lewis acid B(C₆F₅)₃ is not only a highly effective and water tolerant catalyst, the "disfavored" deprotonation of H₂O-B(C₆F₅)₃ adductis possibly playing an important role in reductive amination reaction. To clarify in detail the actual role of water in the reductive amination reaction under the "moist" conditions would enable the further development of FLP and related catalyzed reactions.
- frustrated Lewis pairs,
- B(C₆F₅)₃,
- hydrosilanes,
- reductive amination,
- water
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沈阳化工大学材料科学与工程学院沈阳 110142

Reductive Amination by One Pot Reaction of Aldehydes and Alkoxyamines Catalyzed by B(C6F5)3

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通讯作者: 陈斌, bchen63@163.com

Reductive Amination by One Pot Reaction of Aldehydes and Alkoxyamines Catalyzed by B(C₆F₅)₃