Alkyne groups

Novel fluonnated 2,2-bis(trifluoromethyl)dioxolanes containing alkyne groups [97] have been synthesized from hexafluoroacetone and either 1,4-dibro-mo-2-butene-orpropargylic alcohol [92]. 

The four structures with three double bonds (third row) and the one with four double bonds are the most plausible Lewis structures, (b) The structure with four double bonds fits these observations best, (c) +7 the structure with all single bonds fits this criterion best, (d) Approaches (a) and (b) are consistent but approach (c) is not. This result is reasonable because oxidation numbers are assigned by assuming ionic bonding. 2.109 The alkyne group has the stiffer C—H bond because a large force constant, k, results in a higher-frequency absorption. 

What determines the propensity of cyclization of the different diethynylated complexes Looking carefully at the monomers, there are three variables which could influence the formation of cycles as opposed to linear polymers. One is the angle a between the two alkyne arms. The second is the parameter /, which indicates how far the two alkyne groups are apart at their origin, while the third is the parameter the bulk of the monomer. 

Two S/P ligands derived from camphor, CamPHOS and MeCamPHOS were also developed by these authors for the diastereoselective coordination to alkyne-hexacarbonyldicobalt complexes (Scheme 10.68). These two ligands were converted in good yields into their borane-protected forms. The influence of the alkyne group (R) on their coordination to dicobalt-hexacarbonyl-alkyne complexes was evaluated. It was shown that MeCamPHOS ligand provided a... 

An example, where two C-C-bonds are formed and one C-C-bond is broken is the synthesis of the tricycle 3-285, which has some similarity with the eudesmane framework 3-286, developed by Kilburn and coworkers (Scheme 3.72) [113]. Thus, exposure of the easily accessible methylenecyclopropyl-cyclohexanone 3-281 to samarium(II) iodide led to the generation of ketyl radical 3-282, which builds up a six-membered ring system with simultaneous opening of the cyclopropane moiety. Subsequent capture of the formed radical 3-283 by the adjacent alkyne group afforded the tricycle 3-285 via 3-284 as a single diastereoisomer in up to 60% yield. It should be noted that in this case the usual necessary addition of HMPA could be omitted. 

Co-catalyzed transformations are concerned mainly with the [2+2+2] cycloadditions of three alkyne groups to give arenes. Another important reaction is the [2+2+1] cycloaddition of alkynes, alkenes and CO to give cyclopentenones, which is the well-known as Pauson-Khand reaction [272]. 

Figure 17.10 Propargylamine can be used to add an alkyne group to amine-reactive reagents, such as the NHS ester group on the biotin-PEGj compound.

Figure 17.14 An expressed protein containing a thioester intein tag that was subsequently modified by native chemical ligation to contain an alkyne group then can be labeled using an azido-fluorescein probe by the click chemistry reaction in the presence of Cu1+.

Dissolve a second protein to be functionalized with alkyne groups at a concentration of l-10mg/ml in PBS. 

The two saturated rings of the cannabinoid nucleus are formed with the correct stereochemistry at C-6, C-6a and C-lOa but without selectivity at C-9 in a single acid-catalysed cyclisation step from the phenol 51. Stabilisation of a cationic intermediate by the alkyne group is proposed to account for the facile cyclisation . 

Subsequently, high chemoselectivity and enantioselectivity have been observed in the asymmetric epoxidation of a variety of conjugated enynes using fructose-derived chiral ketone as the catalyst and Oxone as the oxidant. Reported enantioselectivities range from 89% to 97%, and epoxidation occurs chemoselectively at the olefins. In contrast to certain isolated trisubstituted olefins, high enantioselectivity for trisubstituted enynes is noticeable. This may indicate that the alkyne group is beneficial for these substrates due to both electronic and steric effects. 

In the late 1970s, Kirchhoff at Dow Chemical Company developed the use of benzocyclobutenes in polymer synthesis and modification. These efforts culminated in 1985 with the issuance of the first patent describing the use of benzocyclobutene in the synthesis of high-molecular-weight polymer.27 Similar work that involved a thermosetting system based on Diels-Alder cycloaddition between terminal benzocyclobutene and alkyne groups,28,29 was reported separately and independently by Tan and Arnold.28 Since these initial discoveries, the field of benzocyclobutene polymers has expanded rapidly and benzocyclobutene chemistry constitutes the basis of a new and versatile approach to the synthesis of high-performance polymers for applications in the electronics and aerospace industries.30... 

More recently, tetranuclear complexes, related to those previously obtained for both ruthenium and osmium, have been obtained for iron, and their structures have been established by X-ray analysis 118). The reported adducts are [Fe4(CO)11(RC2R1)2] (R = H, R1 = Me, Et, n-Pr R = R1 = Me), and are obtained in very low yield (<1%). For R = H, R1 = C2H5, the structure is shown in Fig. 16. This involves a distorted tetrahedral metal system with the two alkyne groups bonding in a manner similar to that observed for the "butterfly molecule [Co4(CO)10(EtC2Et)] 119). 

If the acceptor molecule contains both an alkene and an alkyne group, hydrostannation occurs at the alkyne moiety. 1,6-Enynes undergo ring closure initiated by addition to the alkyne, as shown by the fate of the deuterium in Equation (26).108... 

TO PARALLEL DISPOSITION OF AN ALKYNE GROUP BRIDGING TWO METAL CENTRES... 

Campidelli et al. have synthesized interesting linear and hyperbranched porphyrin polymers from CNTs via copper-catalyzed alkyne-azide cycloaddition (CuAAC) [122], Zinc porphyrin monomers containing an azide group and one or three alkyne groups were synthesized and chemically bound to alkyne functionalized SWCNTs via CuAAC. Depending upon the number of alkyne functionalities either linear (single alkyne) or dendrimer-like (triple alkyne) porphyrin polymers were produced (Fig. 5.9) [122],... 

Main-chain manipulation offers an opportunity to dramatically change the electronic and physical properties of the PAEs. Popular approaches are the introduction of meta linkages into the polymers, the introduction of aromatic hydrocarbons other than benzene, the introduction of heterocycles, and the substitution of a fraction of the connecting alkyne groups by double bonds. The last strategy leads to polymers that are hybrids between PPEs and PPVs. 

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