Preparation of 2,2-disubstituted azepanes was accomplished from N-tert-butoxy(N-Boc)-2-phenylazepane by treatment with butyllithium then electrophilic quench. The lithiation was followed by in situ ReactIR spectroscopy and the rate of rotation of the carbamate was determined by variable temperature (VT)-NMR spectroscopy and by DFT studies. Most electrophiles add α to the nitrogen atom but cyanoformates and chloroformates gave ortho-substituted products. Cyclic carbamates were formed from an aldehyde or ketone electrophile. Kinetic resolution with sparteine was only poorly selective. Removal of the Boc group promoted cyclization to a homoindolizidine or an isoindolinone.

中文翻译：

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锂化-取代 N-Boc-2-苯氮杂

2,2-二取代氮杂环庚烷的制备是由 N-叔丁氧基 (N-Boc)-2-苯基氮杂环庚烷通过用丁基锂处理然后亲电猝灭来完成的。锂化之后是原位反应红外光谱，氨基甲酸酯的旋转速率由变温 (VT)-NMR 光谱和 DFT 研究确定。大多数亲电子试剂在氮原子上添加 α，但氰基甲酸酯和氯甲酸酯产生邻位取代的产物。环状氨基甲酸酯由醛或酮亲电子试剂形成。用 sparteine 进行动力学拆分的选择性很差。Boc 基团的去除促进环化为高吲哚里西啶或异吲哚酮。