Triquinacene substituted derivatives

Oxidative cleavage of the organic fragment from the metal is possible using Ce and gives the tricyclic rearrangement product (34) in very high yields (equation 15) 45,46 The tetranitrile, (34), prepared in this manner has been used as a key intermediate in the synthesis of chiral 2-substituted triquinacene derivatives.51... 

Similar intramolecular cycloadditions of cyclic alkenes containing alkynyl substitution have been explored by Serratosa in the 3-(3-butynyl)cyclopentene series. The product in this case is a triquinacene derivative, a tricyclo[S.2.1.0 - 0](ig( ane. Since the targets in Serratosa s studies required functionalization of all three five-membered rings, all cycloaddition substrates utilized contained varying degrees of sub-... 

Centropolyindanes constitute a complete family of arylaliphatic polycyclic hydrocarbons containing several indane units. Mutual fusion of the five-membered rings leads to three-dimensional, carbon-rich molecular frameworks bearing a central carbon atom, such as benzo-annelated [3.3.3]propellanes, triquinacenes, and [5.5.5.6]- and [5.5.5.5]fenestranes. In this review, the structural concept of centropolyindanes is contrasted to other fused indane hydrocarbons. Besides the syntheses of the parent centropolyindanes and recently described related indane hydrocarbons, the preparation of a large variety of bridgehead and arene substituted centropolyindanes is presented including strained, heterocyclic, and centrohexacyclic derivatives. In appropriate cases, the particular reactivity and some structural features of these unusual, sterically rigid polycyclic compounds are pointed out. 

Substituted cw-trishomobenzene derivatives have been prepared and found to give the monocyclic triene rapidly. But perhaps the most spectacular example is that of the methane-capped material, diademane, which gives triquinacene with log k = 14.6 - 31600/2.3/ r (Scheme 10.69). 

Cadieux JA, Buller DJ, Wilson PD (2003) Versatile route to centro-substituted triquinacene derivatives synthesis of 10-phenyltriquinacene. Org Lett 5 3983-3986... 

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