Reaction of Aryl and Vinyl

The Rh2(DOSP)4 catalysts (6b) of Davies have proven to be remarkably effective for highly enantioselective cydopropanation reactions of aryl- and vinyl-diazoacetates [2]. The discovery that enantiocontrol could be enhanced when reactions were performed in pentane [35] added advantages that could be attributed to the solvent-directed orientation of chiral attachments of the ligand carboxylates [59]. In addition to the synthesis of (+)-sertraline (1) [6], the uses of this methodology have been extended to the construction of cyclopropane amino acids (Eq. 3) [35], the synthesis of tricyclic systems such as 22 (Eq. 4) [60], and, as an example of tandem cyclopropanation-Cope rearrangement, an efficient asymmetric synthesis of epi-tremulane 23 (Eq. 5) [61]. 

Ligand. Used for Pd-catalyzed reactions of aryl and vinyl halides and triflates. Also for Kumuda coupling reactions. See Dppe for a similar reagent. 

The palladium-catalyzed reaction of aryl- and vinyl-tin reagents with stereochemically defined allyl chlorides proceeds with overall retention of configuration, indicating that the second step, entailing interaction of the iT-allylpalladium complex and the organotin, proceeds by transmetallation and reductive elimination (attack at Pd, retention) (equations 166 and 167).142145 Comparable results were obtained with cyclic vinyl epoxides and aryltins.143... 

In 1971, a year before the groups of Corriu and Kumada [5] independently reported the groundbreaking work on the topic of nickel-catalyzed cross-coupling reactions of aryl and vinyl halides with Grignard reagents, Tamura and Kochi described an iron-catalyzed vinylation reaction of Grignard reagents with vinyl halides (Scheme 5.1) [6]. 

A stereoselective synthesis of substituted tetrahydrofurans (69) via Pd-catalysed reactions of aryl and vinyl bromides with y -hydroxy terminal alkenes (68) has been described. This transformation affords trans-2,5- and frara-2,3-disubstituted tetrahydrofurans with up to >20 1 dr. This methodology also provides access to bicyclic and (g) spirocyclic tetrahydrofuran derivatives in good yield with 10-20 1 dr. The effect of... 

A number of di- or trimerization reactions of aryl and vinyl halides, which are mechanistically related to those in Eqs. 47-49, have been reported. Interestingly, in the reaction of o-tert-hutyl- and o-methoxyiodobenzenes, the aliphatic C-H bonds in the orf/20-substituents are intramolecularly activated to give di- and trimerized products, respectively, with good yields (Eqs. 51 and 52) [111-114]. These reactions can also be applied to the cross-coupling of different halides. Dimerization of vinyl halides has also been reported [115,116]. 

Okuro, K., Furuune, M., Miura, M., Nomura, M. Copper-catalyzed coupling reaction of aryl and vinyl halides with terminal alkynes. 

The coupling reaction of aryl and vinyl iodides, bromides, and triflates with organotin compounds can also be very effectively conducted using palladium on carbon as a source of Pd . The yield and rate of... 

Hiyama and Mori introduced the Mizoroki-Heck-type reaction of aryl- and vinyl-... 

Intramolecular Reaction of Aryl and Vinyl Halides Heck-, Suzuki-, and Stille-Type Reactions... 

Substitution of aryl and vinylic halides. Dieck and Heck have reported a reaction of aryl and vinylic bromides and iodides with olefins catalyzed by palladium acetate and 2 eq. of triphenylphosphine that is related to the reaction mentioned above. New olefins are formed by replacement of the vinylic hydrogen of the original olefin by the Ar or R group of the halide. 

Xu, Li, Xia, Huang, and co-workers have reported a range of P—C bond-forming processes involving the coupling of aryl and vinyl halides with phosphorus(V) reagents. For example, they have reported the cross-coupling reaction of aryl and vinyl bromides... 

F.i. Reactions of Aryl and Vinyl Halides with Metal Carbonylates... 

Iyer, S., Ramesh, C. and Ramani, A. (1997) Ni(0) catalyzed reactions of aryl and vinyl halides with alkenes and alkynes. Tetrahedron Lett., 38, 8533-6. 

Tanaka and his associates demonstrated for the first time how to use non-volatile ionic liquids (ILs) as solvents in palladium-catalyzed carbonylations [163], In the case of alkoxycarbonylation of bromobenzene, higher yields were obtained when 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4] was used as the reaction medium compared with standard conditions. And the selectivity for the monocarb-onylation of iodobenzene with t -PrOH or Et2NH was significantly enhanced by [bmim][BF4]. After separation of the products, the solvent-catalyst system was easily recycled and exhibited catalytic activity up to seven times. Since then the replacement of traditional solvents with quaternary ammonium halides, imidazoli-um- or pyridinium-derived ILs has gained increasing importance [164—173]. Recently, the phosphonium salt IL trihexyl(tetradecyl)phosphonium bromide has proven to be an effective reaction medium for various carbonylation reactions of aryl and vinyl bromides or iodides under mild conditions (Scheme 2.17) [174]. 

The original cross-coupling reactions of aryl and vinyl halides with boronic acid coupling partners have been extensively developed since their inception. Over the past few years several interesting adaptions have expanded the scope of the original coupling protocol, below are just a few recent examples of systems that have harnessed the Suzuki-Miyaura protocol to access enantio-enriched coupling products. 

In recent work that is related to the organocuprate chemistry discussed above, Miura et al. have reported the Cul-catalyzed reaction of aryl and vinyl iodides with terminal alkynes, and of aryl iodides with active methylene compounds. ... 

Fahey DR (1970) Reaction of aryl and vinyl halides with nickel(O) complexes. J Am Chem Soc 92 402-404... 

An interchange between the two pathways can be accomplished using appropriate reaction conditions. For example, the cationic pathway can be obtained in the Heck reaction of aryl and vinyl halides by employing halide scavenging additives such as silver or thallium salts forming the cationic palladium(II) intermediate subsequent to the oxidative addition, as reported by Hallberg and coworkers [78]. 

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