Compounds of Nitrogen, Sulphur, and Selenium

Mc2NCOCH2Li to steroidal ketones provides the /S-hydroxy-NN-dimethylcarb-oxamides and analogous reactions of Mc2NS02CH2Li with steroidal epoxides and ketones provide the y-hydroxy- and )3-hydroxy-sulphonamides. ° 

Both the (20S)- and, in contrast to earlier work, the (20/ )-amino-21-hydr-oxypregn-5-enes (125) can be diazotized with nitrous acid to give acceptable yields 

Lobe-Tobo and F. Khuong-Huu, Bull. Soc. chim. France, 1976, 1835. 

A -compounds (130) with CH2NO2 leads to the nitrocyclopropanes (131) by Michael addition and elimination of HBr. Various transformations of the la-nitromethyl-3-oxo-compounds (132) include its conversion into the la-formyl-3-oxo-compound (133), which on hydride reduction was converted into the tetra-hydrofuran (134).  

Oxidation of the 7/3-phenylselenyl-A -steroids (135) with H2O2 gave the two configurationally stable R- and 5-selenoxides (136) and (137) respectively which react by independent pathways. The R-isomer (136) underwent the familiar 2,3-sigmatropic shift leading, after solvolysis, to the allylic alcohol (138) whereas the 5-isomer (137) gave the A -diene owing to pronounced steric hindrance to the 

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