Studies On The Chemistry Of Centropolyindane And Total Synthesis Of Hyacinthacines And Gibbilimbols

This thesis is concerned with the studies on the chemistry of centropolyindane, a novel family of polycyclic hydrocarbon, novel cyclophane and a series of building blocks were synthesized. As well as the total synthesis of hyacinthacines and gibbilimbols, the construction of C-glycoside by Stille coupling. It consists of the following five parts:First, a review of literature on the synthesis of tribenzotriquinacene and its derivatives was revealed. In which the construction of tribenzotriquinacene and the extension were introduced in details, novel hydrocarbons were achieved on the extension at the different parts of tribenzotriquinacenes.In chapter 2, the study on the chemistry of centropolyindanes was introduced in detail. An efficient method for the extension of tribenzotriquinacenes and all-cis-[5.5.5.5]fenestranes by Stille coupling reaction was developed, and a series of novel three-dimensional frameworks were synthesized successfully. Additionally, an efficient method for the regioselective chloromethylation of tribenzotriquinacenes was developed, and the C_3v-symmetrical hexakis(chloromethyl)tribenzotriquinacene was prepared as key interemediate, the first examples of novel bowl-shaped tribenzotriquinacenes bearing three dithiametacyclophane units within their arene peripheries were synthesized, which are host-molecules for the small guest-molecules. Further studies on the arrangement of these molecules at the solid state and the theoretic calculations were also given. Attempts to synthesize globular cyclophane based on tribenzotriquinacenes were processed. Based on all of them, novel organic networks such as molecular container compounds, dendritic architectures and complex organometallic compounds become accessible. And based on the key intermediate, a series of tribenzotriquinacen derivatives were also synthesized by S_n2 reactions bearing hexakis groups such as Br, N₃, OH, SH and so on, which are potential building blocks for constructing novel supermolecules by selfassembling.In Chapter 3 and 4, the total synthesis of hyacinthacines and gibbilimbols were described respectively. Starting from the readily available D-glucose as the chiral pool, the chiral centers of D-glucose were well used and rebuilt, and two polyhydroxylated pyrrolidines were prepared with high yields and stereoselectivity. Thus, carbon-chain lengthening by a suitable functionalized two more carbon atoms fragment, followed by simultaneous reduction and intramolecular cyclization led to 5-epi-hyacinthacine A₄ and hyacinthacine A₆. Studies on the total synthesis of gibbilimbols by Wittig or Ramberg-Backlund reaction as key step were described, and Gibbilimbol A-D and a derivative (natural product) were synthesized.At last, the construstion of C-glycoside by Stille coupling was described, which involved in the use of CuI as catalyst and 4,7-diphenyl-1,10- phenanthroline as ligand was developed.