Computational and Synthetic Studies with Tetravinylethylenes

Abstract

Computational and experimental studies offer fresh insights into the neglected tetravinylethylene class of compounds. Both the structures and the outcomes of exploratory reactions of the parent hydrocarbon are predicted and explained in detail through high-level composite ab initio MO G4(MP2) computational studies.

A Broad‐Spectrum Synthesis of Tetravinylethylenes

“…The first synthesis of TVE, a landmark contribution from the classical era of unsaturated hydrocarbon chemistry, was reported by Skattebøl and co‐workers in the 1960s . We recently disclosed the first preparatively useful approach to TVE, a one‐step, multi‐gram scale synthesis, and demonstrated that the hydrocarbon is bench‐stable when stored as a neat liquid . The one‐step synthesis of TVE (Scheme , 1 a ) utilized a Pd 0 ‐catalyzed fourfold Stille cross‐coupling sequence between tetrachloroethylene 2 and vinyltributylstannane 3 a .…”

“…The one‐step synthesis of TVE (Scheme , 1 a ) utilized a Pd 0 ‐catalyzed fourfold Stille cross‐coupling sequence between tetrachloroethylene 2 and vinyltributylstannane 3 a . In addition to the parent TVE, five symmetrically substituted TVEs 1 b were similarly prepared using substituted alkenyltributylstannanes 3 b in the exhaustive Stille cross‐coupling process …”

“…As a starting point for future synthetic applications, the parent TVE has been shown to rapidly generate multi‐cyclic systems . Additionally, the hybrid through‐/cross‐conjugated structure of the TVE unit represents the smallest organic four‐directional branch point in a possible conducting molecular wire .…”

“…When performed in the presence of dienophile N‐tert ‐butylmaleimide 8 , a subsequent endo ‐mode cycloaddition occurs, with approach to the less sterically encumbered π‐diastereoface of [4]dendralene 7 . The two non‐equivalent semi‐cyclic dienes of [4]dendralene 7 (highlighted in different colors in Scheme ) are expected to be more reactive than the cyclohexadiene site, and the phenyl‐substituted diene is preferred over the 1‐naphthyl‐substituted site. Overall, this operationally trivial domino sequence generates densely functionalized decalin 9 , with three new C−C bonds, six contiguous stereocenters, and a cyclic [3]dendralene subunit that invites additional synthetic manipulation…”

“…[1][2][3] We recently disclosed the first preparatively useful approacht oT VE, ao ne-step, multi-gram scale synthesis, and demonstrated that the hydrocarbon is bench-stable when stored as an eat liquid. [4,5] The one-step synthesiso fT VE (Scheme 1, 1a)u tilized aP d 0 -catalyzed fourfold Stille crosscoupling sequence betweent etrachloroethylene 2 and vinyltributylstannane 3a.Ina ddition to the parentTVE, five symmetri-cally substituted TVEs 1b were similarly prepared using substituted alkenyltributylstannanes 3b in the exhaustive Stille cross-couplingp rocess. [4,5] As as tarting point for future synthetic applications, the parentT VE has been shownt or apidlyg enerate multi-cyclic systems.…”