Intermolecular reactions coupling reaction table

Wong reported that stoichiometric amounts of copper(I) chloride alone can promote the intramolecular Stille coupling (equation 138)243. In fact, copper(I)-mediated reaction was cleaner and faster compared with that catalysed by Pd(0) species. Selected examples of intermolecular Stille coupling reactions leading to dienes (Table 25)236a,242b 244, polyenes (Table 26)245 and macrocyclizations (Table 27)246 are given in the respective tables. 

TABLE 1. Fast Intermolecular Heck Coupling Reactions Under Microwave Irradiation s... 

IV.2.1.1 SCOPE, MECHANISM, AND OTHER ASPECTS OF THE HECK REACTION 1163 TABLE 2. Intermolecular Heck Coupling Reactions... 

The additive-modified catalyst mixture developed for intramolecular olefin coupling is sufficiently active to catalyze the analogous intermolecular reaction. A variety of five-membered N-heterocydes can be catalytically alkylated at the C-2 position (Table 2) [8], Additional functional groups on the heterocyde[15] (Table 2, Entry 1) and on the olefin (Table 3) are well tolerated. Products corresponding to linear addition are usually obtained exclusively, even when the olefin is rapidly isomerized under the reaction conditions. 

When the reaction was carried out in 50% aqueous THF, more benzhydrol (53) was produced than in the solid state (Table 15-12). Since the reaction in the solid state is a high-concentration process, the intermolecular reaction of 51 would occur more easily to produce mainly the coupling product 52. As the water content in aqueous THF decreases, the ratio of 52 53 increases. For example, when the coupling reaction of 51 (X=Br) with Zn-ZnCl2 was carried out at room tempera-... 

Early on, Heck and co-workers found that intra- and intermolecular coupling reactions of haloalkenes with alkenes in the presence of secondary amines gave allylamines.t t Apparently, an intermediate 7r-allylpalladium complex is formed by rearranganent of the (7-homoallylpalladium intermediate (see above, B.ii) and in turn attacked by the nitrogen nucleophile. Excellent yields of tertiary aUylamines are obtained in this three-component coupling (Scheme As far as the outcome is concerned, analogous inter-intra- as well as fully intramolecular processes have been estabhshed (Scheme 30 see Table... 

In order to confirm this assumption the authors performed the experiments inO Table 9 [113]. Equimolar amounts of armed and disarmed donors 64, and 200 or 202b were allowed to compete for one equivalent of acceptor 215 under the agency of NIS. When one equivalent of NIS was used the major product obtained was that of glycosylation of armed NPG 216, thus in agreement with a process of intermolecular halonium transfer and preferred reaction of the more reactive donor (O Table 9, entries i, iii). When the amount of NIS was increased to three equivalents, the observed ratio of compounds 216 and 217 indicated enhanced coupling of the disarmed donor (O Table 9, entries ii, iv), thus in agreement with the proposed rationalization for the regiopreferences observed in the three-component reactions. 

As seen in Table 6.1, diolide (236) can be formed during cyclization, by reaction of an initial intermolecular coupling product, the co-substituted carboxylate [X—(CH2)n—CO2—(CH2)nC02 j. The... 

Shono and coworkers achieved electroreductive intra- and intermolecular couplings of ketones and nitriles in 2-propanol solutions containing Et4NTos using Sn cathodes at controlled potential (-2.8 V SCE). Intramolecular coupling of cyclic y- and (5-cyano ketones, besides good to excellent yields, proved to be cis stereoselective when a-hydroxy ketones with bicyclo[3.3.0] or [4.3.0] skeletons were formed. When the reactions were carried out at 65 °C instead of 25 °C, dehydration of hydroxy ketones occurred and the corresponding a,jS-unsaturated ketones were obtained. The presence of alkyl or 2-ethoxycarbonyl substituents did not hinder the cyclization. In Table 13 some representative examples are shown. 

A Pt(II)-Ni(II) compound 216 was synthesized via straightforward salt metathesis reaction (Scheme 10.88) [151]. The Pt(II)-Ni(II) bond length in 216 is 2.570(1) A (Entry 1, Table 10.16), and a wetik intermolecular Pt-Pt interaction was found to be responsible for the formation of a head-to-tail dimer structure of 216. A magnetism study revealed 216 to be one of the first examples of antrferromagnetic coupling through an unbridged Pt-Pt interaction. 

McMurry reactions will be presented in the following order intermolecular, intramolecular, mixed (tandem) couplings of aldehydes and ketones, and finally keto ester, oxoamide, and acetal couplings. All the compounds which serve as illustrations are listed in Tables 6.1-6.10, along with the titanium reagents and solvents used for their preparation and the yields of isolated products where not specified, the reactions were performed at solvent reflux temperature. 

Catalytic intermolecular coupling of alkene and alkyne is quite a challenging task. Nevertheless, cyclopentadienyl rutheniumcomplexes are able to catalyze alkyne-alkene coupling (an Alder-ene type reaction) to a mixture of the re-gioisomeric products 120 and 121 (Scheme 52). The most efficient catalysts are the complexes 78 or 53. The latter is more reactive. The scope of the reaction with respect to substituents attached to the both reactants is enormous ester, hydroxy, nitrile, ether, amino, and arylhalide groups are tolerated. Both terminal and internal alkynes and alkenes can be used. Some typical examples are summarized in Table 24 [67,69]. 

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