Tert-Butylisocyanide, reaction with

The variety of educts and products of the higher MCRs is illustrated here. Product 72 (Scheme 1.18) is formed from the five functional groups of lysine, benzaldehyde, and tert-butylisocyanide. The synthesis of 73 is achieved with hydrazine, furanaldehyde, malonic acid, and the isocyano methylester of acetic acid, compound 74 results from the reaction of benzylamine, 5-methyl-2-furanaldehyde, maleic acid mono-ethylester, and benzylisocyanide. ° Zhu et al. prepared a variety of related products, such as, 75, from (9-amino-methyl cinnamate, heptanal, and a-isocyano a-benzyl acetamides. 

Zirconium-benzyne complexes have been used rather extensively in organic synthesis.8 45 For this purpose, one particularly important characteristic of zirconium-aryne complexes is that olefin insertion into the Zr—C bond occurs stereospecifically. Thus, when generated in situ, the zirconium-benzyne complex (45) reacts with cyclic alkenes to give exclusively the cis-zirconaindanes (46), which upon treatment with electrophiles provide access to a variety of m-difunctionalized cycloalkanes (47-49) (Scheme 5).46 For example, carbonylation of intermediate 46 affords tricyclic ketone 49, reaction with sulfur dichloride gives thiophene 48, and reaction of 46 with tert-butylisocyanide followed by I2 gives 47 via 50 and, presumably, intermediate 51 [Eq. (12)]. 

Scheme 7.5 Preparation of bis(l,5-cyclooctadiene)platinum(0) (19) and its reactions with ethene to tris(ethene)platinum(0) (20) and with tert-butylisocyanide to the trinuclear platinum cluster 21 (R = fBu)...

The major difference between the reactions of the isoelectronic carbon monoxide and tert-butylisocyanide with 2 comes, most probably, from the different stability of the hypothetical obtainable rhodium cations. The complex [Rh(CNBu )4]+, a stable and well-known cation, allows the formation of 14, while the relatively low stability... 

Caution. Chromium, molybdenum and tungsten hexacarbonyls are volatile solids (Cr > Mo > W) and like all metal carbonyl compounds should be considered to be toxic. tert-Butylisocyanide has a pungent odor, and although many isocyanides are reported to exhibit no appreciable toxicity to mammals, it should still be handled with care. Carbon monoxide is evolved in these reactions and being an odorless, toxic gas, care should be exercised to carry out the reactions in an efficient ventilation hood with the apparatus venting into a well-ventilated region of the hood. 

Andersen RA (1979) Dialkylbis[bis(trimethylsilyl)amido]zirconium(IV) and -ha iium(IV). Preparation and reaction with carbon dioxide and tert-butylisocyanide. Inorg Chem 18 2928-2932... 

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