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1,1,3-Tris -1 -alkenes

A more stable tris(alkene) complex of Pd uses norbornene tris(bicyclo[2.2.1]heptene) ... [Pg.40]

The reactivity of [Mo(PMe3)4()] -ethene)2] has been much studied and, for example, the tris-alkene-containing compound [Mo(PMe3)()]"-H2C=CH-COOMe)3] is prepared on treatment with H2C=CH-COOMe and it has been crystallographically characterized (Figured). The structure... [Pg.2804]

Dissolution of the frans-cycloheptene-CuOTf complex in cycloheptene and evaporation of the solvent delivers a tris alkene complex of CuOTf containing one frans-cycloheptene and two cis-cycloheptene ligands. Heating frans-cycloheptene-CuOTf in neat c/s-cycloheptene delivers the trans,anti,trans,anti,trans trimer (eq 16). Experiments with c/s-cycloheptene-<4 show that the cyclotrimerization involves only frans-cycloheptene molecules, although the reaction is accelerated by the presence of cis-cycloheptene. A likely explanation for these observations is concerted template cyclotrimerization of a tns-trans-cycloheptene-CuOTf complex formed by ligand redistribution (eq 16). ... [Pg.160]

The synthesis of a range of [Pt(NN)(Ti-alkene)R(X)] complexes (NN = bipy, phen etc. R = Me, Et, Ph X = halide) has been achieved by addition of RX to [Pt(NN)( n-alkene)].57i The five-coordinated tris-alkene species [PtMeCK n-C IiiK n-diene)] (diene = 3,7-dimethylenebicyclo-[3.3.1]-nonane) have also been prcpared. " as have the complexes [PtMe(Ti3-C3H5)L] for a range of phosphines L heating, or treatment with MeLi, causes cyclometallation of the phosphine... [Pg.265]

Reaction of 2,6-dimethyl pyridine with the tris(alkene) dinickel species [(77, 77 -(l,6-heptadiene)Ni)]2(/, 77 r/ -(l,6-heptadiene)) gives the intense yellow compound Ni(77, 77 -(l,6-heptadiene)(2,6-dimethylpyridine). The solid-state structure of this complex showed that the pyridine is oriented perpendicular to the plane of Ni(olefin)2, implying significant vr-backbonding from Ni into the pyridine tt orbitals. The reaction of this bis(alkene) species with alkynes gives the corresponding bis(alkyne) complexes vide infra). [Pg.138]

Physical properties of highly branched polymers are different from their linear analogs and have many potential applications in medicine and nanoengineering. Dendritic polymers with monodispersed composition and weU-defined tree-like structures are even attractive. Efficient reactions are required, and thiol-ene was used by Hawker and coworkers to prepare dendrimers starting from a tris-alkene core 2,4,6-triallyloxy-l,3,5-triazine. 1-Thioglycerol was used to introduce two hydroxy groups via UV-irradiated thiol-ene reaction, which was carried out at room temperature for 30 min. Due to the efficient nature of thiol-ene chemistry and less byproducts, hydroxy-terminated dendrimers... [Pg.265]

While we can make the trans nitro-alkene B easily enough, the cis-nitro alkene A would present problems, so let s try route b ... [Pg.87]

The first was from a CA article [81]. Various alkenes, styrene and cycloalkenes were tried. But a more followable method is the following [82]. The supported salt of NaNs-AljOs was made by mixing the NaNs with the alumina in water then evaporating the mixture under vacuum in a water bath until dry ... [Pg.185]

A major difficulty with the Diels-Alder reaction is its sensitivity to sterical hindrance. Tri- and tetrasubstituted olefins or dienes with bulky substituents at the terminal carbons react only very slowly. Therefore bicyclic compounds with polar reactions are more suitable for such target molecules, e.g. steroids. There exist, however, several exceptions, e. g. a reaction of a tetrasubstituted alkene with a 1,1-disubstituted diene to produce a cyclohexene intermediate containing three contiguous quaternary carbon atoms (S. Danishefsky, 1979). This reaction was assisted by large polarity differences between the electron rich diene and the electron deficient ene component. [Pg.86]

Thallation of aromatic compounds with thallium tris(trifluoroacetate) proceeds more easily than mercuration. Transmetallation of organothallium compounds with Pd(II) is used for synthetic purposes. The reaction of alkenes with arylthallium compounds in the presence of Pd(Il) salt gives styrene derivatives (433). The reaction can be made catalytic by use of CuCl7[393,394], The aryla-tion of methyl vinyl ketone was carried out with the arylthallium compound 434[395]. The /9-alkoxythallium compound 435, obtained by oxythallation of styrene, is converted into acetophenone by the treatment with PdCh[396]. [Pg.83]

The cyclization to form very congested quaternary carbon centers involving the intramolecular insertion of di-, tri-, and tetrasubstituted alkenes is particularly useful for natural products synthesis[l36-138], In the total synthesis of gelsemine, the cyclization of 166 has been carried out, in which very severe steric hindrance is e.xpected. Interestingly, one stereoisomer 167... [Pg.152]

Formic acid behaves differently. The expected octadienyl formate is not formed. The reaction of butadiene carried out in formic acid and triethylamine affords 1,7-octadiene (41) as the major product and 1,6-octadiene as a minor product[41-43], Formic acid is a hydride source. It is known that the Pd hydride formed from palladium formate attacks the substituted side of tt-allylpalladium to form the terminal alkene[44] (see Section 2.8). The reductive dimerization of isoprene in formic acid in the presence of Et3N using tri(i)-tolyl)phosphine at room temperature afforded a mixture of dimers in 87% yield, which contained 71% of the head-to-tail dimers 42a and 42b. The mixture was treated with concentrated HCl to give an easily separable chloro derivative 43. By this means, a- and d-citronellol (44 and 45) were pre-pared[45]. [Pg.430]

The unsaturated c.vo-enol lactone 17 is obtained by the coupling of propargylic acetate with 4-pentynoic acid in the presence of KBr using tri(2-furyl)-phosphine (TFP) as a ligand. The reaction is explained by the oxypalladation of the triple bond of 4-pentynoic acid with the ailenyipailadium and the carbox-ylate as shown by 16, followed by reductive elimination to afford the lactone 17. The ( -alkene bond is formed because the oxypalladation is tnins addition[8]. [Pg.455]

Heck type vinylation of 4-bromo-l-(4-methylphenylsulfonyl)-indole proceeds in good yield with such alkenes as methyl acrylate, styrene and N-vinylphthalimide using Pd(OAc)2 (5 mol%) and tri-o-tolylphosphine as the... [Pg.141]

Despite numerous attempts the alkene 3 4 di tert butyl 2 2 5 5 tetramethyl 3 hexene has never been synthesized Can you explain why Try mak mg a space filling model of this compound... [Pg.200]

The Fiiedel-Ciafts alkylation of aiomatics with the lesonance-stabihzed ttichloiocyclopiopenium ttiflate offers a synthetic pathway to ttiaiyl cyclopiopenium salts (26). The ttichloiocyclopiopenium ion has also been shown to undergo Friedel-Crafts reaction with alkenes and alkynes to give trivinyl and tri(halovinyl) cyclopiopenium ions. [Pg.553]

Manufacture and Processing Alkylphenols of commercial importance are generally manufactured by the reaction of an alkene with phenol in the presence of an acid catalyst. The alkenes used vary from single species, such as isobutylene, to compHcated mixtures, such as propylene tetramer (dodecene). The alkene reacts with phenol to produce mono alkylphenols, dialkylphenols, and tri alkylphenols. The mono alkylphenols comprise 85% of all alkylphenol production. [Pg.62]

Bromine monofluoride [13863-59-7], BrF, can be prepared by the direct reaction of Br2 and F2, but because it readily disproportionates it has never been prepared in pure form (57). However, BrF can be prepared in situ by the reaction of Br2 with AgF in benzene (58) or by the reaction of A/-bromoacetamide and HF in ether (59). BrF adds to simple alkenes at room temperature to give products of trans-addition. Bromine trifluoride [7787-71-5], BrF, can be formed from gaseous fluorine and Hquid bromine (60). Bromine pentafluoride [7789-30-2], BrF, is formed from the reaction of BrF vapor with gaseous fluorine at 200°C (60). The tri- and pentafluorides are commercially available. As strong fluorinating agents they are useful in... [Pg.292]

Pyrazoles are formed when the diazo compounds react with alkynes or with functionalized alkenes, viz. the enols of /3-diketones. Pyrazolenines (353 Section 4.04.2.2.1) are isolated from disubstituted diazomethanes. Many pyrazoles, difficult to obtain by other methods, have been prepared by this procedure, for example 3-cyanopyrazole (616) is obtained from cyanoacetylene and diazomethane (7iJCS(C)2i47), 3,4,5-tris(trifiuoromethyl)pyrazole (617) from trifluorodiazoethane and hexafluoro-2-butyne (8lAHC(28)l), and 4-phenyl-3-triflylpyrazole (618 R =H) from phenyltriflylacetylene and diazomethane (82MI40402). An excess of diazomethane causes iV-methylation of the pyrazole (618 R = H) and the two isomers (618 R = Me) and (619) are formed in a ratio of 1 1. [Pg.282]

Intramolecular alkylnitrene addition to an alkenic moiety situated S,e to the electron deficient center has been utilized for the preparation of bi- and tri-cyclic aziridines (Scheme 11) (68JA1650). Oxidation of the primary alkylamine can be effected cleanly with NCS, LTA or mercury(II) oxide. [Pg.87]

Most frequent are oxidations of alkenes that can be converted to a series of compounds such as epoxides, halohydnns and their esters, ozonides (1,2,4 tri-oxolanes), a-hydroxyketones, a-hydroxyketone fluorosulfonates, ot-diketones, and carboxylic acids and their denvatives... [Pg.321]

Table 3. Addition of tra/is-ChlorotetrafIuoro(tri-f1uoromethyl)sulfur to Alkenes [75]... Table 3. Addition of tra/is-ChlorotetrafIuoro(tri-f1uoromethyl)sulfur to Alkenes [75]...
The behavior of strained,/Zuorimiret/ methylenecyelopropanes depends upon the position and level of fluorination [34], l-(Difluoromethylene)cyclopropane is much like tetrafluoroethylene in its preference for [2+2] cycloaddition (equation 37), but Its 2,2-difluoro isomer favors [4+2] cycloadditions (equation 38). Perfluoromethylenecyclopropane is an exceptionally reactive dienophile but does not undergo [2+2] cycloadditions, possibly because of stenc reasons [34, 45] Cycloadditions involving most possible combinations of simple fluoroalkenes and alkenes or alkynes have been tried [85], but kinetic activation enthalpies (A/f j for only the dimerizations of tetrafluoroethylene (22 6-23 5 kcal/mol), chlorotri-fluoroethylene (23 6 kcal/mol), and perfluoropropene (31.6 kcal/mol) and the cycloaddition between chlorotnfluoroethylene and perfluoropropene (25.5 kcal/mol) have been determined accurately [97, 98] Some cycloadditions involving more functionalized alkenes are listed in Table 5 [99. 100, 101, 102, 103]... [Pg.780]

In 1909, Patemo and Chieffi noted that mixtures of tri- or tetra-substituted olefins and aldehydes formed trimethylene oxides when exposed to sunlight. Biichi later repeated Patemo s experiments by irradiating 2-methyI-2-butene in the presence of benzaldehyde, butyraldehyde, or aeetophenone and rigorously purifying and identifying the resulting products. The reaction thus bears the name of its two primary pioneers and has come to represent any photo-catalyzed [2 + 2] electrocyclization of a carbonyl and an alkene. [Pg.44]

Employing protocol V with the methanesulfonamide catalyst 122, a 93 7 er can be obtained in the cyclopropanation of cinnamyl alcohol. This high selectivity translates well into a number of allylic alcohols (Table 3.12) [82]. Di- and tri-substi-tuted alkenes perform well under the conditions of protocol V. However, introduction of substituents on the 2 position leads to a considerable decrease in rate and selectivity (Table 3.12, entry 5). The major failing of this method is its inability to perform selective cyclopropanations of other hydroxyl-containing molecules, most notably homoallylic alcohols. [Pg.138]

In the next step, one of the borane-hydrogens is transferred to a sp -carbon center of the alkene and a carbon-boron bond is formed, via a four-membered cyclic transition state 6. A mono-alkyIborane R-BH2 molecule thus formed can react the same way with two other alkene molecules, to yield a trialkylborane R3B. In case of tri- and tctra-substituted alkenes—e.g. 2-methylbut-2-ene 7 and 2,3-dimethylbut-2-ene 9—which lead to sterically demanding alkyl-substituents at the boron center, borane will react with only two or even only one equivalent of alkene, to yield a alkylborane or mono alky Iborane respectively ... [Pg.170]

The Best results are obtained with cA-alkenes however, the epoxidation of tri-and tetra-substituted double bonds is also possible. Because of its versatility, the Jacobsen-Katsuki epoxidation is an important method in asymmetric synthesis. [Pg.256]

Steric strain (Sections 3.7) The strain imposed on a molecule when two groups are too close together and try to occupy the same space. Steric strain is responsible both for the greater stability of trans versus cis alkenes and for the greater stability of equatorially substituted versus axially substituted cyclohexanes. [Pg.1251]


See other pages where 1,1,3-Tris -1 -alkenes is mentioned: [Pg.51]    [Pg.176]    [Pg.947]    [Pg.716]    [Pg.122]    [Pg.51]    [Pg.18]    [Pg.406]    [Pg.147]    [Pg.263]    [Pg.481]    [Pg.521]    [Pg.334]    [Pg.208]    [Pg.69]    [Pg.153]    [Pg.156]    [Pg.29]    [Pg.46]   
See also in sourсe #XX -- [ Pg.16 ]




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Alkenes tris ligands

Tri-Substituted Alkenes

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