A modular approach to N1-vinyl benzotriazoles by azide–aryne cycloadditions and Julia–Kocienski reactions is described. Reactions of azidomethyl phenyl-1H-tetrazol-5-yl (PT) sulfide with arynes gave methyl(PT-sulfanyl)-substituted benzotriazoles in 68–89% yields. Oxidation of the sulfides to the sulfones gave the benzotriazole-substituted Julia–Kocienski reagents. Olefination reactions of aldehydes and a ketone with reagents derived from benzyne, 2,3-naphthyne, and 4,5-dimethoxybenzyne precursors proceeded to give various N1-vinyl benzotriazole derivatives. Olefination stereoselectivities are tunable for electron-rich aldehydes, but not for electron-deficient aldehydes and alkanals, where they proceed with good to excellent Z-stereoselectivity.

A highly modular approach to N-substituted 4-(1-fluorovinyl)triazoles is described. In situ desilylation and Cu-catalyzed ligation reaction of TMS-protected α-fluoropropargyl benzothiazole sulfone with aryl, alkyl, and metallocenyl azides furnished second-generation Julia-Kocienski reagents in good to excellent yields. Condensation reactions of these reagents with aldehydes can be tuned to yield E or Z-alkenes selectively. Under mild conditions with DBU as base, reactions of aldehydes furnished E-alkenes as the major isomer. On the other hand, in condensations with LHMDS as base and in appropriate solvents, both aldehydes and ketones reacted to yield fluoroalkenes with Z-selectivity. Stereochemical assignment to E/Z olefins obtained in the reaction of a ketone with two Julia reagents was performed via X-ray crystallographic analysis and comparisons of NMR data. The method allows efficient and ready diversification of N1-substituent and substituents at the double bond.

Alkyl, aryl, and metallocenyl azides are tolerated for the preparation of the Julia-Kociensky substrates. Conditions for condensation reactions of the latter with alkyl and aryl aldehydes as well as cyclic and acyclic ketones are developed which provide preferentially E or Z isomeric 4-fluorovinyl-1,2,3-triazoles. The selectivity is strongly influenced by the carbonyl component, but not by the triazole substrate. -(KUMAR, R.; SINGH, G.; TODARO, L. J.; YANG, L.; ZAJC*, B.; Org. Biomol. Chem. 13 (2015) 5, 1536-1549, http://dx.

A new approach to the title compounds by azide—aryne cycloaddition and Julia—Kocienski reaction is described.