Stereoselective addition of carbamates to unsaturated systems by means of mercury(II) nitrate. Synthesis of saturated nitrogen‐containing heterocycles

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Abstract
The aminomercuration of dienes with carbamates and mercury(II) nitrate affords, after in situ demercuration with sodium borohydride, stereoselectively saturated nitrogen‐containing heterocycles. Thus, the corresponding amidomercuration‐demercuration of 1,4‐ or 1,5‐hexadiene, and diallyl ether gives respectively N‐alkoxycarbonyl cis‐2,5‐dimethylpyrrolidines and trans‐3,5‐dimethylmorpholines. From 1,5‐cyclooctadiene 9‐alkoxycarbonyl‐9‐azabicyclo[3.3.1]‐ and [4.2.1]‐nonanes (molar ratio ca. 1:1) are obtained. By amidomercuration‐demercuration of N‐allylurethane cis‐N,N'‐bis(ethoxycarbonyl)‐2,5‐dimethylpiperazine is obtained. The intermolecular amidomercuration of unsaturated systems results stereochemically opposite to the same aminomercuration process.
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