Allylic compounds, cross-metathesis

Allylboronates are attractive reagents for the highly diastereoselective ally-lation of carbonyl compounds. A sequential cross-metathesis-allylation reaction has recently been developed by Grubbs et al. [88c] and by Miyaura et al. [103]. The sequence is illustrated in Scheme 23 for the formation of homoallylic alcohol 114 from allylboronate 112, acetal 113, and benzaldehyde [88c]. 

Two repeated exposures of resin 38 to the catalyst (9% mol) for 18 h in dichloromethane at room temperature afforded the expected allyl lactoside in an encouraging isolated yield of 81% from resin 35 (90% per step). Traces of dimerized compounds resulting from cross-metathesis were detected as the only side products. Extension of the oligosaccharide chain was subsequently performed first by deacetylation (excess NaOMe in 4/1 CH2Cl2/MeOH at r.t.) and glycosylation with known lactosyl donor 40 in conditions similar to those mentioned above. Cleavage was performed twice as described above, but with a reduced reaction time of 6 h in this case tetrasaccharide 42 was isolated in 51% yield from 35 (84% per step). No dimerized products were detected. 

Grubbs used (4a) to efficiently install functional groups that might otherwise be added via C H activation or allylic oxidation pathways (Scheme 12). Among the breadth of compound types accessible through these cross metathesis strategies were substituted vinyl-phosphonic, boronic, and carbonyl esters, which were synthesized in good to excellent yields. ... 

Summary Two catalytic reactions, i.e. silylative coupling (mms-silylation) (SC) catalyzed by complexes containing or generating Ru-H and/or Ru-Si bonds (I, II, V, VI) and cross-metathesis (CM) catalyzed by mthenium-carbene (i.e. 1st and 2nd generation mthenium Grubbs catalyst (ID, IV)) of vinyl and allyl-substituted hetero(N,S,B)organic compounds with conunercially available vinyltrisubstituted silanes, siloxanes, and silsesquioxane have been overviewed. They provide a universal route toward the synthesis of well-defined molecular compounds with vinylsilicon functionality. 

On the other hand, our recent study on the highly efficient cross-metathesis of vinyltrialkoxy-and vinyltrisiloxy-silanes with various olefins, for example, with styrene [12] allyl eth [13] and esters [14] as well as octavinylsilsesquioxane [IS] with several olefins have opened a new opportunity for the use of alkene-cross-metathesis in the synthesis of unsaturated organosilicon compounds (see also Refs. [5] and [6]). In this p r new examples of the two reactions involving hetero(N,S,B)organic olefins have been overviewed. 

Mechanistic implications of a general cross-metathesis of vinylsilicon with allyl-substituted heteroorganic compounds have been studied in detail for the reaction with allyl alkyl ethers [13]. The detailed NMR study of the stoichiometric reaction of Grubbs catalyst with allyl-n-butyl ether has provided information on individual steps of the catalytic cycle. A general mechanism of the cross-metathesis of vinyltri(alkoxy, siloxy)silanes (as well as octavinylsilsesquioxane) with 3-heteroatom-containing 1-alkenes in the presence of ruthenium carbene is shown in Scheme 5. 

Cross metathesis of chiral allylic alcohol or amine moieties and styrene to create phenyl analogues of the parent compounds was achieved using (4a). The phenyl group, in conjugation with the parent molecule, lends a stronger extinction coefficient to the molecules, making the species more amenable for analysis by circular dichroism. ... 

A number of research groups have utilized the strategy outlined above to synthesize benzene ring-containing compounds. For example, Kotha successfully employed it for the synthesis of phenylalanine derivatives [36]. Starting with aUcyne 87 and the aUcene allyl acetate, cross-enyne metathesis afforded diene 88. This readily underwent a Diels-Alder reaction with dimethyl acetylenedicarboxylate (DMAD) to afford cyclohexene 89. Aromatization of these compounds with DDQ subsequently furnished the phenylalanine 90 in good yield (Scheme 17.17). 

Building on these results, Hanessian and co-workers devised an efficient protocol for the isomerisation of terminal olefins with minimal self-dimerisation or cross-metathesis by employing methanol to generate hydride complex 33 in situ from its parent 10. The procedure was successfully applied to a variety of allylic compounds, including O- and A-allyl ethers, and cleanly afforded the corresponding propenyl species as EjZ isomeric mixtures, without any further isomerisation or conjugation in the cases of ketones, esters and lactams. 

Allylsilanes can be prepared by a wide array of methods, including (1) the reaction of allyl metals with ClSiRs, (2) the reaction of silylanions (MSiRs) with allylic substrates, (3) the Kumada coupling of Me3SiCH2MgBr with vinyl halides, catalyzed by Pd or Ni species, (4) the Wittig reaction of P-silylated Wittig reagents, (5) the cross-metathesis of olefins with allylsilanes, and (6) the reductive silylation of unsaturated compounds. ... 

A variety of a-spirolactones and lactams from 2-diazo-l,3-dicarbonyl compounds, (homo)allylic alcohols or amines and acrylic derivatives, in a single synthetic operation by a Wolff rearrangement/a-oxo ketene trapping/cross metathesis/ intramolecular Michael addition sequence has been obtained by Boddaert et al. (2011). 

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