Chemistry of N-haloamines. 25. Amination of acyclic and cyclic alkanes with trichloramine-aluminum chloride

Studies on intramolecular cycloadditions involving 3-oxidopyridinium

“…Finely divided lithium metal (15 mg, 2.1 mmol) was added to a stirred solution of the epoxide (75 mg, 0.38 mmol) in dry ethylenediamine (5 ml) at room temperature and the mixture was then heated to 50 "C for 1 h. The solution was cooled and the excess of lithium destroyed by the careful addition of water (1 ml). The mixture was diluted with ether (20 ml) and the organic phase washed with water (3 x 30 ml), dried, and evaporated to give an oil which was distilled (bulb-to-bulb) to give 1 l-aza-4~,11-dimethyl-4a-hydroxy-1a,7a-bicyclo[5.4.0]undecme (28) (56 mg, 74%), v, , , 3 370, 2 930, 1 440, 1 130, and 1 030cm-'; tiH(9O MHz) 1.25 (3 H, s, Me), 1.4-1.9 (14 211.193 60).…”

“…The presence of the N-methyl group serves to clutter the aza bridged face of the structure leading to addition across both faces of the enone. In the subsequent reaction with methylmagnesium bromide to produce the alcohol, the methyl ketone (11) gives only one product, assigned as the anti-alcohol (13),f whilst the ketone (12), in which the two methyl groups both serve to inhibit attack from the aza-bridged face, gives not only the anti-alcohol (15) 8, but also the syn-alcohol (14), in a ratio of 1 : 2 respectively. For this system, the saturated ketone (16) gives only the anti-alcohol…”

Thermal, Catalytic Conversion of Alkanes to Linear Aldehydes and Linear Amines

“…In addition, we describe the conversion of simple alkanes to high-value siloxy-terminated linear aldehydes via a sequence of alkane silylation and carbonylation, an unprecedented transformation for 2-fold catalytic alkane functionalizations. Moreover, this dual-catalyst system was successfully applied to alkane aminomethylations, which represent the first example of regioselective conversion of n -alkanes to linear amines (Figure C) …”