Imidoyl iodides

O-Acylated or mesylated oximes such as the ethyl carbonate of acetophenone-oxime 1772 react with TIS 17, with Beckmann rearrangement to the imidoyl iodide 1773, which adds phenylmagnesium bromide in situ to give 61% of the sec-... 

The synthesis of analogous iminoacyl complexes by isonitrile insertion into linear alkyl-zirconocene chlorides is also known. In an overall regiospecific hydrocyanation of alkenes, iminoacyls 21 derived from tBuNC or Me3SiCN (as the Me3SiNC isomer) may be treated with I2 to rapidly generate an imidoyl iodide and subsequently the nitrile 22 (Scheme 3.6) [22], Less hindered iminoacyl complexes (e. g. R = Bu, Cy) may be hydrolyzed to afford aldehydes 23 [23]. 

Trifluoroacetimidoyllithiums 75 have been prepared from imidoyl iodides by reaction with n-BuLi at — 78 °C and have been trapped with aldehydes, ketones, epoxides,... 

Imidoyl iodides. Reaction of oxime mesylates (or carbonates) of ketones with (C2H5)2A11 effects Beckmann rearrangement to imidoyl iodides, which can be directly alkylated with Grignard reagents and then reduced (DIBAH) to a-alkylated amines. Examples ... 

Isonitriles add carboxylic acid chlorides to yield oi-oxoimidoyl chlorides (210 equation 117). 1.3.5395,396 With copper catalysis, from perfluorinated alkyl iodides and isonitriles imidoyl iodides (211 equation 118) can be obtained. - Alkenes react with nitriles in the presence of HF or to afford the... 

Chlorine adds to /V-trichlorovinylbenzaldehydeimine to give the yV-benzylideneamide chloride (224) which is in equilibrium with the imidoyl chloride (225 equation 122). The action of trimethylsilyl iodide or diethylaluminum iodide on 0-acylketoximes affords imidoyl iodides (226 equation 123) with excellent yields. ... 

Although imidoyl iodides are chemically labile, their in situ generation from oxime derivatives with trimethylsilyl iodide or diethylaluminum iodide has been ascertained spectroscopically (equation 14). The synthetic utility of these reactive species has been demonstrated by further reacting them with external nucleophiles such as thiolates or Grignard reagents. For example, the imidoyl iodide (28), generated from acetophenone oxime carbonate with trimethylsilyl iodide, is further transformed to ethylthioimidate (29) and a-alkylated amine (30), respectively (Scheme 1 and equation 15). 

Palladium-catalyzed carboalkoxylation of imidoyl iodides 6 provides benzyl [9] and even te/t-butyl[10] esters 7. Asymmetric hydrogenation of the imino moiety of imono esters 7 in a Pd(OCOCF3)2 / (7 )-BINAP / CF3CH2OH system gives enantio-enriched amino esters 8 in 85-91% ee (see Scheme 9.2) [11].The enantioselectivity achieved by the hydrogenation was much better than that by Corey s hydride reduction [12] and was employed for the syntheses of enantiomerically pure A-Boc-(3,(3-difluoroproline benzyl ester 9 (see Scheme 9.3)[13] and enantiomerically enriched A-Boc-P -difluoroglutamic acid benzyl ester [13]. 

Some synthetic applications are shown in Schemes 2.39-2.41. 1,1-Addition of perfluoroalkyl iodides to isonitriles (26) provides perfluoroalkyl imidoyl iodides (27) [24], which have been employed as useful reactive intermediates for trifluoromethylated amino acids and heterocycles [25].Stereo-controlledperfluoroalkylation [26] andbromodifluoromethy-lation [27] of the enolates (28) and (30) give diastereomerically enriched fluoro-building blocks (29) and (31). 

The applicability of tin-mediated radical cyclizations of non-isocyanides to form indoles has been pursued by several other investigators. Uneyama and colleagues reported the tin-mediated deiodination of imidoyl iodides and subsequent indolization (Scheme 1, equation 1) [1], This radical cyclization is also effected photochemically. Bowman and colleagues exploited the tin-promoted radical generation from imidoyl selanides and cyclization to form indoles... 

Yu HB, Huang WY (1998) A novel precursor for per(poly)fluoroalkyl heterocycles from V-aryl per(poly)fluoioalkyl imidoyl iodides. J Fluor Chem 87 69-73... 

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