Isothiocyanates, reaction with Grignard reagents

Xi has developed practical methods for the synthesis of CPDNs 378 by the reaction of 1,4-dilithio-l,3-dienes 379 with carbon dioxide, carbon monoxide, and isothiocyanates (Scheme 6.92a-c) [224]. The dianions 379 are derived from readily available 1,4-diiodo-l,3-dienes 380. In the reaction in Scheme 6.92b, the presence of CuCl plays an important role in the formation of CPDNs. Moreover, the reaction with isothiocyanates affords iminocyclopentadienes (ICPDs) 381 in good yields, which are easily converted to CPDNs by acidic hydrolysis. 1,4-Bis-Grignard reagents 382, easily derived from 1,4-dibromobutadiene 383, react similarly with... 

Aryl isothiocyanates The reaction of arylamines with the reagent affords 5-(A(-aryliinino)-4-chloro-l,2,3-dithiazoles which are decomposed to give ArN=C=S by a Grignard reagent. 

Oxime sulfonates were rearranged in the presence of diisobutylaluminum methyl sulfide to produce methylthioimidates, e.g. (291 equation 155), and methylthiolactim ethers in good yields. The adducts formed in the reaction of Grignard reagents with trimethylsilylmethyl isothiocyanate can be alkylated to furnish the -trimethylsilylmethylthioimidates (292 equation 156). 2.603 Ph,... 

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