Alkenyl-substituted cyclic

The ring-closing enyne metathesis has been used for the synthesis of alkenyl substituted six- and seven-membered cyclic enol ethers (Eq. 88) [144]. The reaction has been proposed as an element of the strategy for preparation of subunits of brevetoxins and ciguatoxins. 

Elaboration of isoxazolines has been used in the synthesis of other heterocycles. Electrophilic cyclization reactions of 5-alkenyl-substituted isoxazolines (150) have been used in the synthesis of cyclic ethers (Scheme 68) (87JA7577 90JOC283). Hydrogenolysis and decarboxylation of the... 

The thermal decomposition of 3-, 4- and 5-alkenyl azides118119 produced, via the intermediate dihydrolriazoles118 12°, a mixture of bicyclic aziridines and imines, but latter predominating. In the presence of a substituent at C-l, the aziridines were obtained as diastereomeric mixtures118. However, if substituted cyclic imines90 92-94-108,121-124 were 0j-,rained, asymmetric induction was achieved in successive reduction steps, e.g., 3-6. 

Linear LC siloxanes have been well known since the end of the seventies [4] and an enormous variety of compounds, including networks, have been synthesized in the meantime [5]. These side-chain polymers are usually synthesized by a well-established standard procedure, that is, the coupling of co-alkenyl substituted mesogenic groups to H-siloxanes with the aid of a Pt catalyst. This concept has been extended to various geometric and chemical classes of backbone siloxanes, linear [6], cyclic [7, 8] and cage-like siloxanes [9], or siloxanes with a great variety of substituents [10]. 

One more carbene-based route to oxapenam derivatives utilizes the Cu-catalyzed decomposition of diazo compounds 547 via cyclic sulfonium ylide 548. The protocol is effective for 5-aryl (80H1999) and 5-heteryl-substituted (82H1597) diazo compounds of type 547. Oida and co-workers succeeded in obtaining oxapenam 549 (33%) by Cu(acac)2-catalyzed transformation of 5-alkenyl-substituted diazo ketones 550. The attempted synthesis of... 

The proton chemical shifts of representative acyclic and cyclic dienamines are collected in Tables 14-16. Examination of the Tables show that alkenyl substitution at C(l) or C(2) of an enamine produces also deshielding of the olefinic protons, as seen by comparing the <5H(2) values of compound 149 (3 3.75, 3.85 ppm Table 11) with those of the analogous cross-conjugated dienamine 105 ( 3.85, 4.05 ppm Table 14). The chemical shift of the vinylic protons of dienamines correlate only partially with the charge calculated for the corresponding olefinic carbons . In the linear conjugated... 

Bearing in mind these requirements many classes of unconjugated dienes have been investigated. These include alicyclic, monocyclic, alkenyl substituted monocyclic, fused-ring cyclic, bridged-ring bicy-clic and tricyclic dienes. Of all the specific dienes investigated three have reached commercial status ... 

Scheme 16 Copper-phosphinamine-catalysed ECA of alkenyl aluminium reagents (prepared by hydroalumination with DIBAL-H) to P-substituted cyclic enones by Alexakis [48,49]...

The reaction of a halide with 2-butene-1,4-diol (104) affords the aldehyde 105, which is converted into the 4-substituted 2-hydroxytetrahydrofuran 106, and oxidized to the 3-aryl-7-butyrolactone 107[94], Asymmetric arylation of the cyclic acetal 108 with phenyl triflate[95] using Pd-BINAP afforded 109, which was converted into the 3-phenyllactone 110 in 72% ee[96]. Addition of a molecular sieve (MS3A) shows a favorable effect on this arylation. The reaction of the 3-siloxycyclopentene 111 with an alkenyl iodide affords the. silyl... 

This procedure illustrates a general method for the stereoselective synthesis of ( P)-disubstitnted alkenyl alcohols. The reductive elimination of cyclic /3-halo-ethers with metals was first introduced by Paul3 and one example, the conversion of tetrahydrofurfuryl chloride [2-(chloromethyl)tetrahydrofuran] to 4-penten-l-ol, is described in an earlier volume of this series.4 In 1947 Paul and Riobe5 prepared 4-nonen-l-ol by this method, and the general method has subsequently been applied to obtain alkenyl alcohols with other substitution patterns.2,6-8 (I )-4-Hexen-l-ol has been prepared by this method9 and in lower yield by an analogous reaction with 3-bromo-2-methyltetra-hydropyran.10... 

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]. 

Reggelin et al. reported the application of methylated, enantiomerically pure acyclic and cyclic 2-alkenyl sulfoximines 203 for the synthesis of highly substituted aza(poly)cyclic ring systems 204 under complete stereocontrol <06JA4023 06S2224>. 

The intramolecular process has been proposed by Widenhoefer with palladium(ll) catalysts.40 41 Cyclization of alkenyl-1,3-dione 26 proceeds efficiently with commercially available palladium species in dioxane at room temperature (Scheme 8). Such mild conditions allow high tolerance vis-a-vis functionalities, and cyclic products are obtained in good yields. Cyclization, tolerated substitution at the terminal methyl group and at the active methylene. This protocol also allows the reaction of internal olefins with (Z)- or ( )-configuration to occur. 

It is observed that insertion into a zirconacyclopentene 163, which is not a-substituted on either the alkyl and alkenyl side of the zirconium, shows only a 2.2 1 selectivity in favor of the alkyl side. Further steric hindrance of approach to the alkyl side by the use of a terminally substituted trans-alkene in the co-cyclization to form 164 leads to complete selectivity in favor of insertion into the alkenyl side. However, insertion into the zirconacycle 165 derived from a cyclic alkene surprisingly gives complete selectivity in favor of insertion into the alkyl side. In the proposed mechanism of insertion, attack of a carbenoid on the zirconium atom to form an ate complex must occur in the same plane as the C—Zr—C atoms (lateral attack 171 Fig. 3.3) [87,88]. It is not surprising that an a-alkenyl substituent, which lies precisely in that plane, has such a pronounced effect. The difference between 164 and 165 may also have a steric basis (Fig. 3.3). The alkyl substituent in 164 lies in the lateral attack plane (as illustrated by 172), whereas in 165 it lies well out of the plane (as illustrated by 173). However, the difference between 165 and 163 cannot be attributed to steric factors 165 is more hindered on the alkyl side. A similar pattern is observed for insertion into zirconacyclopentanes 167 and 168, where insertion into the more hindered side is observed for the former. In the zirconacycles 169 and 170, where the extra substituent is (3 to the zirconium, insertion is remarkably selective in favor of the somewhat more hindered side. 

The reaction of PhS02 with 2-(2 -phenylsulfonyl)-2, 3 -butadienylmalonate 233 affords the five-membered cyclic alkenyl sulfone 235 via a 1,4-addition, intramolecular deprotonation and a SN2 -substitution process [124, 125]. 

The 5-(2-alkenyloxy)thiatriazoles on thermal degradation gave alkenyl isocyanates by a presumed allylic rearrangement of the expected 2-alkenyl cyanates.54 Although the data do not exclude decomposition via intramolecular cyclic attack at the 4-position in the ring followed by very rapid decomposition of the 4-substituted thiatriazolines, these... 

Three types of reaction systems have been designed and applied for the enantioposition-selective asymmetric cross-coupling reactions so far. First example is asymmetric induction of planar chirality on chromium-arene complexes [7,8]. T vo chloro-suhstituents in a tricarhonyl("n6-o-dichlorobenzene)chromium are prochiral with respect to the planar chirality of the 7t-arene-metal moiety, thus an enantioposition-selective substitution at one of the two chloro substituents takes place to give a planar chiral monosubstitution product with a minor amount of the disubstitution product. A similar methodology of monosuhstitution can be applicable to the synthesis of axially chiral biaryl molecules from an achiral ditriflate in which the two tri-fluoromethanesulfonyloxy groups are enantiotopic [9-11]. The last example is intramolecular alkylation of alkenyl triflate with one of the enantiotopic alkylboranes, which leads to a chiral cyclic system [12], The structures of the three representative substrates are illustrated in Figure 8F.1. 

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