Beilstein J. Org. Chem.2019,15, 1236–1256, doi:10.3762/bjoc.15.121
groups like CH3 and OMe does only partially. Both steric and electronic effects can be explained from the reactivity of the diimineintermediate. An electron-withdrawing group promotes the nucleophilic attack of the ketoimine N by increasing the partially positive charge of the imine C. In general
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Graphical Abstract
Figure 1:
Structures of natural steroids of A) animal and B) plant origin.
Beilstein J. Org. Chem.2014,10, 259–270, doi:10.3762/bjoc.10.21
hydrazine (Me2C=N–NH2) was obtained. The channel involves two likely proton-transfer routes. However, it was found that the base-free reaction was unlikely at the N2 extrusion step from the isopropyl diimineintermediate (Me2C(H)–N=N–H). Two base-catalyzed reactions were investigated by models of the ketone
product. For both ketone substrates, the diimines undergoing E2 reactions were found to be key intermediates.
Keywords: acetone; acetophenone; DFT calculations; diimineintermediate; reduction reaction; transition states; Wolff–Kishner; Introduction
The Wolff–Kishner (W-K) reduction is an organic
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From hydrazone, the hydrazone anion is formed, which was first suggested by Seibert [6][7]. From the anion, there are two routes (a) and (b). In (a), the proton is [1,3]-shifted to give an isomer anion, R1(R2)HC–N=N(−). In (b), a diimineintermediate R1(R2)HC–N=N–H is generated [6][7][8]. Both routes
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Graphical Abstract
Scheme 1:
The Wolff–Kishner (W-K) reduction. DEG, diethylene glycol (HO–C2H4–O–C2H4–OH), is usually used as a...