Iodides alkenes

The catalyst The amount of catalyst required in an aryl bromide or iodide alkene substitution varies widely with the reactants and the reaction conditions. Most examples reported have used 1-2 mol % of palladium salt relative to the aryl halide, but much lower amounts are sufficient in some instances. In an extreme case, where very reactive p-nitrobromobenzene was added to the very active alkene, ethyl acrylate and sodium acetate was the base in DMF solution at 130 C with a palladium acetate-tri-o-tolylphos-phine catalyst in 6 h the palladium turned over 134 000 times and ethyl p-nitrocinnamate was obtained in 67% yield.63... 

In 1989 Curran and co-workers reported on a photocatalytically induced free-radical cyclization leading to various cyclic, bi-, or polycyclic carbocycles (fused and spiro) via isomerization of unsaturated iodides (alkenes, alkynes) [63]. This corresponds to the nonreductive variant of the tin hydride method. Under sunlight irradiation and in the presence of 10 mol% hexabutylditin, a-iodo esters, ketones, and malonates are efficiently transformed via an iodide atom transfer chain mechanism (eq. (4)). 

Bauer and Maier synthesized the benzolactone 538, which has the core structure of salicylihalamide A, using intramolecular Suzuki reaction.228 Hydrobora-tion of the alkenyl iodide-alkene 537 with 9-BBN and subsequent Suzuki reaction in the presence of a palladium catalyst gave the macrolactone 538 in 48% yield (Scheme 160). The hydroboration proceeded with high diastereoselectivity. 

Another feature of the Pd—C bonds is the excellent functional group tolerance. They are inert to many functional groups, except alkenes and alkynes and iodides and bromides attached to sp carbons, and not sensitive to H2O, ROH, and even RCO H. In this sense, they are very different from Grignard reagents, which react with carbonyl groups and are easily protonated. 

In the reaction of Q,/3-unsaturated ketones and esters, sometimes simple Michael-type addition (insertion and hydrogenolysis, or hydroarylation, and hydroalkenylation) of alkenes is observed[53,54]. For example, a simple addition product 56 to methyl vinyl ketone was obtained by the reaction of the heteroaromatic iodide 55[S5]. The corresponding bromide affords the usual insertion-elimination product. Saturated ketones are obtained cleanly by hydroarylation of o,/3l-unsaturated ketones with aryl halides in the presence of sodium formate, which hydrogenolyses the R—Pd—I intermediate to R— Pd—H[56]. Intramolecular hydroarylation is a useful reaction. The diiodide 57 reacts smoothly with sodium formate to give a model compound for the afla-toxin 58. (see Section 1.1.6)[57]. Use of triethylammonium formate and BU4NCI gives better results. 

The diazonium salts 145 are another source of arylpalladium com-plexes[114]. They are the most reactive source of arylpalladium species and the reaction can be carried out at room temperature. In addition, they can be used for alkene insertion in the absence of a phosphine ligand using Pd2(dba)3 as a catalyst. This reaction consists of the indirect substitution reaction of an aromatic nitro group with an alkene. The use of diazonium salts is more convenient and synthetically useful than the use of aryl halides, because many aryl halides are prepared from diazonium salts. Diazotization of the aniline derivative 146 in aqueous solution and subsequent insertion of acrylate catalyzed by Pd(OAc)2 by the addition of MeOH are carried out as a one-pot reaction, affording the cinnamate 147 in good yield[115]. The A-nitroso-jV-arylacetamide 148 is prepared from acetanilides and used as another precursor of arylpalladium intermediate. It is more reactive than aryl iodides and bromides and reacts with alkenes at 40 °C without addition of a phosphine ligandfl 16]. 

The alkynyl iodide 150 undergoes the oxidative addition to form an alky-nylpalladium iodide, and subsequent insertion of an alkene gives the conjugated enyne 151 under phase-transfer conditions[120]. 

Intramolecular reaction can be used for polycyclization reaction[275]. In the so-called Pd-catalyzed cascade carbopalladation of the polyalkenyne 392, the first step is the oxidative addition to alkenyl iodide. Then the intramolecular alkyne insertion takes place twice, followed by the alkene insertion twice. The last step is the elimination of/3-hydrogen. In this way, the steroid skeleton 393 is constructed from the linear diynetriene 392(276]. 

However, in the reaction of 1-alkenylboranes with aryl- or 1-alkenyi iodides. 2-aryl-l-alkenes 648 are obtained as the main products. When Pd metal produced from Pd(OAc)2 as a catalyst and EtjN as a weak bu.se are u.sed. abnormal products are formed. On the other hand, normal products 649 are obtained by using NaOH[5l7]. 

The reaction of perfluoroalkyl iodides with alkenes affords the perfluoro-alkylated alkyl iodides 931. Q.a-Difluoro-functionalized phosphonates are prepared by the addition of the iododifluoromethylphosphonate (932) at room temperature[778], A one-electron transfer-initiated radical mechanism has been proposed for the addition reaction. Addition to alkynes affords 1-perfluoro-alkyl-2-iodoalkenes (933)[779-781]. The fluorine-containing oxirane 934 is obtained by the reaction of allyl aicohol[782]. Under a CO atmosphere, the carbocarbonylation of the alkenol 935 and the alkynol 937 takes place with perfluoroalkyl iodides to give the fluorine-containing lactones 936 and 938[783]. 

The reachvity of the hydrogen halides reflects their ability to donate a proton Hydrogen iodide IS the strongest acid of the hydrogen halides and reacts with alkenes at the fastest rate... 

Among the hydrogen halides only hydrogen bromide reacts with alkenes by both electrophilic and free radical addition mechanisms Hydrogen iodide and hydrogen chlo ride always add to alkenes by electrophilic addition and follow Markovmkov s rule Hydrogen bromide normally reacts by electrophilic addition but if peroxides are pres ent or if the reaction is initiated photochemically the free radical mechanism is followed... 

Hydrogen bromide (but not hydrogen chloride or hydrogen iodide) adds to alkynes by a free radical mechanism when peroxides are present m the reaction mixture As m the free radical addition of hydrogen bromide to alkenes (Section 6 8) a regioselectiv ity opposite to Markovmkov s rule is observed... 

This reaction is called the Smmons-Smith reaction and is one of the few methods avail able for the synthesis of cyclopropanes Mechanistically the Simmons-Smith reaction seems to proceed by a single step cycloaddition of a methylene (CH2) unit from lodomethylzmc iodide to the alkene... 

What alkenes would you choose as starting materials in order to prepare each of the following cyclopropane derivatives by reaction with lodomethylzmc iodide ... 

Methylene transfer from lodomethylzmc iodide is stereospecific Substituents that were cis in the alkene remain cis m the cyclopropane... 

Methylene transfer from lodo methylzinc iodide converts alkenes to cyclopropanes The reaction is a stereo specific syn addition of a CH2 group to the double bond... 

Simmons-Smith reaction (Section 14 12) Reaction of an alkene with lodomethylzmc iodide to form a cyclopropane denvative... 

The iodination reaction can also be conducted with iodine monochloride in the presence of sodium acetate (240) or iodine in the presence of water or methanolic sodium acetate (241). Under these mild conditions functionalized alkenes can be transformed into the corresponding iodides. AppHcation of B-alkyl-9-BBN derivatives in the chlorination and dark bromination reactions allows better utilization of alkyl groups (235,242). An indirect stereoselective procedure for the conversion of alkynes into (H)-1-ha1o-1-alkenes is based on the mercuration reaction of boronic acids followed by in situ bromination or iodination of the intermediate mercuric salts (243). 

Both ( )- and (Z)-l-halo-l-alkenes can be prepared by hydroboration of 1-alkynes or 1-halo-l-alkynes followed by halogenation of the intermediate boronic esters (244,245). Differences in the addition—elimination mechanisms operating in these reactions lead to the opposite configurations of iodides as compared to bromides and chlorides. 

Electrophilic attack on the sulfur atom of thiiranes by alkyl halides does not give thiiranium salts but rather products derived from attack of the halide ion on the intermediate cyclic salt (B-81MI50602). Treatment of a s-2,3-dimethylthiirane with methyl iodide yields cis-2-butene by two possible mechanisms (Scheme 31). A stereoselective isomerization of alkenes is accomplished by conversion to a thiirane of opposite stereochemistry followed by desulfurization by methyl iodide (75TL2709). Treatment of thiiranes with alkyl chlorides and bromides gives 2-chloro- or 2-bromo-ethyl sulfides (Scheme 32). Intramolecular alkylation of the sulfur atom of a thiirane may occur if the geometry is favorable the intermediate sulfonium ions are unstable to nucleophilic attack and rearrangement may occur (Scheme 33). 

S-Alkylthiiranium salts, e.g. (46), may be desulfurized by fluoride, chloride, bromide or iodide ions (Scheme 62) (78CC630). With chloride and bromide ion considerable dealkylation of (46) occurs. In salts less hindered than (46) nucleophilic attack on a ring carbon atom is common. When (46) is treated with bromide ion, only an 18% yield of alkene is obtained (compared to 100% with iodide ion), but the yield is quantitative if the methanesulfenyl bromide is removed by reaction with cyclohexene. Iodide ion has been used most generally. Sulfuranes may be intermediates, although in only one case was NMR evidence observed. Theoretical calculations favor a sulfurane structure (e.g. 17) in the gas phase, but polar solvents are likely to favor the thiiranium salt structure. 

Seven procedures descnbe preparation of important synthesis intermediates A two-step procedure gives 2-(HYDROXYMETHYL)ALLYLTRIMETH-YLSILANE, a versatile bifunctional reagent As the acetate, it can be converted to a tnmethylenemethane-palladium complex (in situ) which undergoes [3 -(- 2] annulation reactions with electron-deficient alkenes A preparation of halide-free METHYLLITHIUM is included because the presence of lithium halide in the reagent sometimes complicates the analysis and use of methyllithium Commercial samples invariably contain a full molar equivalent of bromide or iodide AZLLENE IS a fundamental compound in organic chemistry, the preparation... 

Xenon difluoride is used to prepare methyliodine difluoride from methyl iodide [102, 128] as well as to convert miscellaneous aryl [103, 129, 110] heptafluorapropyl [129], and 2,2,2-trifluoroethyl [103] iodides to the corresponding organo iodine difluorides in yields ranging from 60 to 100% Elemental fluorine transforms aryl iodides to their corresponding aryliodine difluoride turn pounds [131 132], which are known to add fluorine to alkenes ]133] (equation 21)... 

Polymer-bound phenyliodine difluoride, which also has been used as a reagent to add fluorine to alkenes, can be prepared by the addition of xenon difluoride to the polymer [134, 135 136] Methyl iodide is converted to trifluoro methyliodine difluoride by treatment with fluorine at -110 C [137] Perfluoro-alkyliodine tetrafluorides could be synthesized from the perfluoroalkyliodine difluorides and fluorine [138] or chlorine trifluoride [139] Perfluoroalkyl [140] and perfluoroaryl [141] iodides are oxidized to the corresponding iodine difluorides by chlorine trifluoride. 

Allylation of perfluoroalkyl halides with allylsilanes is catalyzed by iron or ruthenium carbonyl complexes [77S] (equation 119) Alkenyl-, allyl-, and alkynyl-stannanes react with perfluoroalkyl iodides 111 the presence ot a palladium complex to give alkenes and alkynes bearing perfluoroalkyl groups [139] (equation 120)... 

The addition of halogenated aliphatics to carbon-carbon double bonds is the most useful type of carbon-carbon bond forming synthetic method for highly halogenated substrates Numerous synthetic procedures have been developed for these types of reactions, particularly for the addition of perfluoroalkyl iodides to alkenes using thermal or photolytic initiators of free radical reactions such as organic peroxides and azo compounds [/]... 

The reaction of perfluoroalkyl iodides with electron donor nucleophiles such as sodium arene and alkane sulfinates in aprotic solvents results in radical addition to alkenes initiated by an electron-transfer process The additions can be carried out at room temperature, with high yields obtained for strained olefins [4 (equations 3-5)... 

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