Alkenes norbornene

Simple alkenes, norbornene and styrene do not undergo cyclopropanation or insertion reactions with cyclopropyl(methoxy)carbene chromium pentacarbonyl complex. However, the conjugated 1-vinylcyclopentene is cyclopropanated under the reaction conditions at the terminal double bond, affording an isomeric mixture trans.cis = 40 60), in 66% yield (equation 72). 

Similar results arc obtained with addition of hydrogen cyanide or deuterium cyanide to dcutcr-ated and nondeuterated alkenes, norbornene and anchored cyclohexenes in the presence of Pd(Diop)2 as the catalyst precursor20-24. Steric requirements in the substrate are crucial. Thus, 7,7-dimethylnorbornene is not hydrocyanated and 4-/m-butylcyclohexene only gives the equatorial product (vide infra)10-24. 

This thermally unstable compound reacts with triphenylphosphine to form the oxide, and with alkenes to form epoxides. Yields of up to 50% epoxide have been obtained using the alkenes norbornene and cyclohexene. Otsuka et al. have recently isolated the bromo analog compound PtBr(OOCOPh)-(PPh3)2 in a pure state and have shown that it will oxidize norbornene to ejco-norbornene epoxide in 40% yield. 

The strained alkene, norbornene 19 has a special place in C-H bond functionalization of (hetero)arenes. Catellani and co-workers have... 

The cyclohexadiene derivative 130 was obtained by the co-cyclization of DMAD with strained alkenes such as norbornene catalyzed by 75[63], However, the linear 2 1 adduct 131 of an alkene and DMAD was obtained selectively using bis(maleic anhydride)(norbornene)palladium (124)[64] as a cat-alyst[65], A similar reaction of allyl alcohol with DMAD is catalyzed by the catalyst 123 to give the linear adducts 132 and 133[66], Reaction of a vinyl ether with DMAD gives the cyclopentene derivatives 134 and 135 as 2 I adducts, and a cyclooctadiene derivative, although the selectivity is not high[67]. 

In a manner analogous to classic nitrile iinines, the additions of trifluoro-methylacetonitrile phenylimine occur regiospecifically with activated terminal alkenes but less selectively with alkynes [39], The nitnle imine reacts with both dimethyl fumarate and dimethyl maleate m moderate yields to give exclusively the trans product, presumably via epimenzation of the labile H at position 4 [40] (equation 42) The nitrile imine exhibits exo selectivities in its reactions with norbornene and norbornadiene, which are similar to those seen for the nitrile oxide [37], and even greater reactivity with enolates than that of the nitnle oxide [38, 41], Reactions of trifluoroacetomtrile phenyl imine with isocyanates, isothiocyanates, and carbodiimides are also reported [42]... 

Early work established that S4N4 forms di-adducts with alkenes such as norbornene or norbomadiene. Subsequently, structural and spectroscopic studies established that cycloaddition occurs in a 1,3-S,S"-fashion. The regiochemistry of addition can be rationalized in frontier orbital terms the interaction of the alkene HOMO with the low-lying LUMO of S4N4 exerts kinetic control. Consistently, only electron-rich alkenes add to S4N4. 

Mutual metathesis of a cyclic and an acyclic alkene provides still more possibilities in synthesizing organic compounds. For instance, cycloalkenes are cleaved by ethene into a,co-dienes. The reaction of 1,5-cyclooctadiene with ethene gives 1,5,9-decatriene (18) norbornene reacts with 2-butene to yield 1,3-dipropenylcyclopentane (30) ... 

Ring strain enhances alkene reactivity. Norbornene, for example, undergoes rapid addition of TFA at 0° C.12... 

Apart from the role of substituents in determining regioselectivity, several other structural features affect the reactivity of dipolarophiles. Strain increases reactivity norbornene, for example, is consistently more reactive than cyclohexene in 1,3-DCA reactions. Conjugated functional groups usually increase reactivity. This increased reactivity has most often been demonstrated with electron-attracting substituents, but for some 1,3-dipoles, enol ethers, enamines, and other alkenes with donor substituents are also quite reactive. Some reactivity data for a series of alkenes with several 1,3-dipoles are given in Table 10.6 of Part A. Additional discussion of these reactivity trends can be found in Section 10.3.1 of Part A. 

Phosphite complexes of platinum(0) have received substantially less attention than have phosphine complexes.44 [Pt P(OC6H4OMe-2)3 3] can be prepared by reduction of the [PtCl2 P-(OC6H4OMe-2)3 2] complex in the presence of the phosphite or by the reaction of the phosphite with Lris(//2-norbornene)platinum(II) 44 Alkene complexes of bis(phosphite)platinum(II) can be prepared in a similar manner to the analogous phosphine complexes. 

AuCl(alkene)] (alkene = m-cyclooctene. norbornene, CHf/o-dicyclopentadiene ) complexes have been obtained by reaction of [AuCl(CO)] with the alkene.2280,2281 The structure of [AuC1(Ci0H12)] shows the ligand //2-bonded to gold via the C=C bond in the norbornene ring and the molecules are associated into dimers through Au Au interactions.2281... 

Most studies on nickel-catalyzed domino reactions have been performed by Ikeda and colleagues [287], who observed that alkenyl nickel species, obtained from alkynes 6/4-41 and a (jr-allyl) nickel complex, can react with organometallics as 6/4-42. If this reaction is carried out in the presence of enones 6/4-43 and TM SCI, then coupling products such as 6/4-44 are obtained. After hydrolysis, substituted ketones 6/4-45 are obtained (Scheme 6/4.12). With cyclic and (5-substituted enones the use of pyridine is essential. Usually, the regioselectivity and stereoselectivity of the reactions is very high. On occasion, alkenes can be used instead of alkynes, though this is rather restricted as only norbornene gave reasonable results [288]. 

The interest in catalyst recyclability has led to the development of biphasic catalysts for hydro-boration.22 Derivitization of Wilkinson s catalyst with fluorocarbon ponytails affords [Rh(P (CH2)2(CF2)5CF3 3)3Cl] which catalyzes FIBcat addition to norbornene in a mixture of C6FnCF3 and tetrahydrofuran (TF1F) or toluene (alternatively a nonsolvent system can be used with just the fluorocarbon and norbornene) to give exo-norborneol in 76% yield with a turnover number up to 8,500 (Scheme 4). Mono-, di- and trisubstituted alkenes can all be reacted under these conditions. The catalyst can be readily recycled over three runs with no loss of activity.23... 

The Pd/MOP combination has proved active for the asymmetric hydrosilylation of cyclic alkenes and dienes. Thus treatment of norbornene with HSiCl3 at 0 °C for 24 h in the presence of 0.01 mol.% of M eO-MOIV[Pd(// -C3H5)Cl]2 gave quantitative yield of evo-2-(trichlorosilyl)norbornane oxidation produced the corresponding alcohol in 93% ee (Equation (12)). Lowering the temperature (to — 20 °C) increased this to a 96% ee. Both mono- and difunctionalization of nbd has proved possible, depending upon the quantity of trichlorosilane used (Scheme 22). In both reactions, extremely good enantioselectivities are observed 113... 

Hydrophosphination of ethyl acrylate using PH3 (R = C02Me, Equation (17)) is catalyzed by a mixture of the zero-valent platinum complexes (72a c), which are formed upon addition of P CH2CH2C02Et 3 to Pt(norbornene)3] (Scheme 44). Failure of these complexes to bring about P H addition to CH2 = CHCF3 indicates that Michael activation of the alkene through I and R effects of the substituents is crucial for catalytic activity in this class of metal complexes.190... 

Similar to the addition of secondary phosphine-borane complexes to alkynes described in Scheme 6.137, the same hydrophosphination agents can also be added to alkenes under broadly similar reaction conditions, leading to alkylarylphosphines (Scheme 6.138) [274], Again, the expected anti-Markovnikov addition products were obtained exclusively. In some cases, the additions also proceeded at room temperature, but required much longer reaction times (2 days). Treatment of the phosphine-borane complexes with a chiral alkene such as (-)-/ -pinene led to chiral cyclohexene derivatives through a radical-initiated ring-opening mechanism. In related work, Ackerman and coworkers described microwave-assisted Lewis acid-mediated inter-molecular hydroamination reactions of norbornene [275]. 

Intermolecular bis-silylation of unactivated alkenes has been achieved initially with a zerovalent platinum catalyst such as Pt(PPh3)4 (Equations (30) and (31)).101 1,2-Difluorotetramethyldisilane undergoes addition to ethylene and norbornene in the presence of Pt(PPh3)4 catalyst at 150 °G to give the corresponding adducts in 95% and 26% yields, respectively. For the addition of 1,2-diphenyltetramethyldisilane to ethylene, Pt(PMe3)4 (33% yield) was found to be more active than Pt(PPh3)4 (4% yield). 

In a manner similar to that of the bis-silylation of internal alkynes shown above, the use of unsymmetrical disilanes with basic / //-phosphines is effective for intermolecular bis-silylation of terminal alkenes (Equations (32) and (33)).6 Although the regioselectivities need to be improved, clean bis-silylations of 1-octene, styrene, and norbornene have been achieved in high yields. 

Addition of disulfides to carbon-carbon double bonds is catalyzed by ruthenium complexes (Equation (71)).204 Even relatively less reactive dialkyl disulfides add to norbornene with high stereoselectivity in the presence of a catalytic amount of Cp RuCl(cod). Diphenyl disulfide adds to ethylene and terminal alkenes under identical conditions (Equation (72)). 

Norbornene also undergoes silastannation from the exo-side under identical conditions (Equation (112)). However, ordinary alkenes such as 1-hexene, styrene, and cyclohexene fail to react with silylstannanes. 

The report by Basset and co-workers on the metathesis of sulphur-containing alkenes using a tungsten alkylidene complex, mentioned previously for the acyclic cross-metathesis reaction (see Sect. 2.2), also contained early examples of ring-opening cross-metathesis of functionalised alkenes [20]. Allyl methyl sulphide was reacted with norbornene in the presence of the tungsten catalyst 5, to yield the desired ring-opened diene 35 (Eq. 29). 

Successful ring-opening cross-metathesis with symmetrical internal acyclic alkenes was, however, achieved by Blechert and Schneider [49]. Reaction of a variety of functionalised norbornene derivatives with fraws-hex-3-ene in the presence of the ruthenium vinylalkylidene catalyst 4 yielded the ring-opened products as predominantly trans-trans isomers (for example Eq. 33). 

A subsequent publication by Blechert and co-workers demonstrated that the molybdenum alkylidene 3 and the ruthenium benzylidene 17 were also active catalysts for ring-opening cross-metathesis reactions [50]. Norbornene and 7-oxanorbornene derivatives underwent selective ring-opening cross-metathesis with a variety of terminal acyclic alkenes including acrylonitrile, an allylsilane, an allyl stannane and allyl cyanide (for example Eq. 34). 

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