.alpha. Addition and ortho metalation of phenyl isocyanide

Synthese und Eigenschaften der 1,3‐Benzazaphosphole

“…Neben dem 2-t-Butyl-3phenyl-1,3-benzazaphosphol, das nach G1. (13) auf vollig anderem Wege zuganglich ist [21], sind mit 16 und anderen auf diese Weise darstellbaren Vertretern nun auch die ersten 3H-isomeren 1,3-Benzazaphosphole bekannt. Cl2H1,NP, (201,2), P: 15,57 (ber.…”

The reactions of lithium trimethysilylmethyls with isocyanides; structures and reactions of the derived lithium 1-azaallyls, β-diketiminates and a 1-azabuta-1,3-dienyl-3-amide

“…They provide a convenient source for synthesising aldehydes, 1,2 ketones, 1,2 α-hydroxy-ketones, 1-4 β-hydroxy-ketones, 2 βhydroxy-acids, 1 α-keto-acids, 1,5 α-amino-acids 6 or heterocycles such as [R(RЈ)COC(H)᎐ ᎐ NC(H)(RЉ)] 7 or [N᎐ ᎐ C(R)X{1,2-C 6 H 4 }] (X = S, PPh, SiMe 2 , GeMe 2 , SnMe 2 ). 4 The lithio aldimine LiC(RЈ)᎐ ᎐ NRЉ (a masked carbanion) was postulated to be an intermediate, but has not been isolated. 1,2,4-6, 8 Our interest in this type of behaviour derives from (i) our earlier studies on the reactions between a lithium trimethylsilylmethyl and an α-H-free nitrile to give lithium 1-azaallyls (e.g.…”

Synthesis of indole derivatives via isocyanides

“…The presence of an appropriate base in the reaction environment has been useful for the oligomerization process. In this way, alkyl lithium reagents and phenyl isocyanide reacted at −78 • C in the presence of TMEDA to yield products of a-addition and ortholithiation, 40 while lower temperatures (−90 • C) and the presence of LiCH(TMS) 2 65 as a base afforded the trimeric N-lithioindole 66 (Scheme 26). 41…”