Reaction of Vinyltitanium(IV) Species Prepared by the Alkylation of Titanium–Vinylcarbene Complexes

Abstract

Vinyltitanium(IV) species prepared by the alkylation of titanium–vinylcarbene complexes with tert-butyl chloride reacted with aldehydes to give allylic alcohols. The reaction of vinyltitanium species with terminal alkynes produced conjugated dienes, in which a vinyl group regioselectively bonded to the unsubstituted side of carbon–carbon triple bond.

Titanocene(II)-Promoted Stereoselective Alkenylation Utilizing (Z)-Alkenyl Sulfones

“…Although there is no decisive experimental evidence that clarifies the mechanism for the formation of the trans-deuteriated olefin d - 12 , the above results might support the alkenylationvia the formation of the alkenyltitanium species 9 (path B). Such alkenylation of alkynes and aldehydes with the alkenyltitanium species generated by the tertiary alkylation of titanium vinylcarbene complexes was reported by us . Indeed, the conjugated diene 5j was obtained in good yields by the reaction of 3a with 2d carried out with the pretreatment of 2d with 1 at 0 °C for 17 h (entry 1, Table ).…”

The Society for Cardiovascular Angiography and Interventions' 27th Annual Scientific Sessions

“…The terminal olefin 48 was obtained by the titanocene(II)‐mediated reaction of the bissulfide 43a with 3‐chloro‐3‐ethylpentane followed by the hydrolysis of the intermediate alkenyltitanium species 49 48. Allylic alcohols and conjugated dienes were obtained by the treatment of the intermediary alkenyltitaniums with aldehydes and alkynes, respectively 49…”