Diene component

Malpass, 1977). Diels-Alder type [2 + 4]-cycloadditions are possible with certain hetero-"ene components (J.R. Malpass, 1977 S.F. Martin, 1980) or with highly reactive o-quinodimethanes as diene components (W. Oppoizer, I978A). 

In Diels-Alder reactions a nitroolefin may function as an electron-deficient ene com-onent or a 1,2-dihydropyridine derivative may be used as a diene component. Both types of iactants often yield cyclic amine precursors in highly stereoselective manner (R.K. Hill, 1962 i. BOchi, 1965, 1966A). 

Lastly, in perfluorobutadiene s codimerization reaction with butadiene, a significant amount of Diels-Alder adduct is obtained, with the perfluorodiene acting as the diene component [125] (equation 105)... 

A hexagonal phase is found at room temperature and atmospheric pressure in some ethylene-propylene copolymers containing a small amount of diene component [86,93]. 

Intramolecular Diels-Alder reactions employing furan as the diene component are an effective step in the synthesis of many natural products, but difficulties are sometimes encountered due to the poor dienic character of the aromatic ring. Using CDs can help to overcome this problem. Thus, when 73 is heated in water at 89 °C for only 6h a 20% epimeric 1 2 mixture of 74 and 75 is... 

Ene reactions tended to occur as alternative reaction pathways to [2 + 4] cycloaddition, especially when sterically bulky silenes had substituents on the sp2-hybridized carbon atom and dimethylbutadiene served as the diene component. In the ene reactions studied the silene acted as the enophile as often as it acted as the ene. 

The quinolizinium ring can behave as the diene component in reverse electron demand Diels-Alder reactions. For example (Equation 1), the reaction between a dienophile generated in situ by acid-catalyzed dehydration of precursor 72 and quinolizinium 73 gave the l,4-ethanobenzo[A]quinolizinium derivative 74 <2001BML519>. 

Dimethyl anthracene and diphenyl isobenzofuran form remarkably stable233 cyclopropanone derivatives (353/354), whilst with other diene components (butadiene, tetracyclone, and fulvene) the primarily formed Diels-Alder adducts either suffer ketalizing attack of the solvent (356 - 357, 359 - 358/360) or undergo irreversible changes such as decarbonylation to 362 or rearrangement to 355. 

In an attempt toward electron-rich and electron-deficient multiple bonds as well as 1,3-dipoles, the triafulvene system may develop functionalization of a dipolarophilic, dienophilic, and diene component. Rigorous proof for a concerted or a stepwise mechanism, e.g. via dipolar intermediates, for any of the numerous reactions investigated cannot be presented. Therefore the following classification has been chosen from a more or less formal point of view. 

In some cases the C /C2 double bond in methylene cyclopropenes and calicenes was found to show dienophilic functionality towards diene components. Thus, di-ethylamino butadiene combines with 497 to give the Diels-Alder adduct 507, whose proton-catalyzed elimination of amine interestingly did not lead to the dibenzo heptafulvalene 508, but to the methylene norcaradiene derivative 509293 ... 

There are few reports about chiral auxiliary-attached diene components due, in part, to the difficulty of the preparation of the modified dienes. Schemes 5-13,12 5-14,12b 5-15,13 and 5 1613 show some selected examples. 

Diels-Alder disconnection will have been eliminated, and the rctrosynthetic search becomes highly focused. Having selected both the transform and the mapping onto the TGT, it is possible to sharpen the analysis in terms of potentially available dienophile or diene components, variants on the structure of the intermediate for Diels-Alder disconnection, tactics for ensuring stereocontrol and/or position control in the Diels-Alder addition, possible chiral control elements for enantioselective Diels-Alder reaction, etc. 

Here again the high reactivity is due to the gain of aromatic stabilization in the adduct. Polycyclic aromatics are moderately reactive as the diene component in Diels-Alder reactions. Anthracene forms adducts with a number of dienophiles. The addition occurs at the centre ring. The naphthalene ring system is much less reactive. 

The diene component is electron rich whereas the dienophile is electron deficient. Electron releasing substituents favour the reaction, while the electron with drawing groups decrease the rate. This may be due to their effect in raising the energy of the dienes HOMO to make it more compatible with the dienophiles LUMO. 

Moving on to vinylallene (2) and its derivatives as substrates, the situation becomes rapidly more complex - and more interesting. The possibility of using vinylallenes as diene components in Diels-Alder additions was recognized many years ago [5]. As shown in Scheme 5.44, the [2+ 4] cycloaddition of a generalized dienophile 283 to 2 yields 3-methylencyclohexene adducts 293. 

Vinylallenes and bisallenes participate in the Diels-Alder-type cycloaddition as the diene component, providing a powerful tool for the construction of complex ring systems. They also undergo thermal electrocydic ring closure to form methylenecy-clobutene derivatives. 

The use of vinylallenes as the diene component in Diels-Alder reactions is very common, thus resulting in their ubiquitous use in natural product synthesis. A vinylal-lene has even been proposed by Schreiber and Kiessling [10] as a biogenetic intermediate in the synthesis of the skeleton of esperamicin A (32 —> 33). Their synthetic approach to esperamicin A (34) was modeled after this biogenetic proposal in which a Type II intramolecular Diels-Alder cycloaddition was used to gain access to the highly unsaturated bicyclic core of 34 (Scheme 19.8) [10]. 

When thiophene dioxide (106) was used as the diene component, true catalysis was observed with 107, affording the capsule bound adduct 108 (equation 32)93. The displacement of a single molecule of adduct by two molecules of starting material is, in principle, disfavored on entropic grounds, but turnover took place in this case due to the poorer affinity of the Diels-Alder adduct for the capsule. The rate enhancement of this reaction, based on the ratio of the half-life for the reaction outside vs inside the capsule, was 10-fold. 

Compared to the application of ordinary conjugated dienes, the use of vinylallenes as diene components is advantageous from the viewpoint of both reactivity and stereoselectivity. The equilibrium between the s-trans and s-cis conformers is more on the side of the s-cis isomer for vinylallenes than it is for 1,3-dienes. Consequently, vinylallenes exhibit a higher reactivity. 

The thermally allowed [8 + 2] cycloaddition reactions may be considered as the 10tt analogs of the Diels-Alder reaction in which the diene component has been replaced by a tetraene component. Like trienes in the [6 + 4] cycloaddition reactions, the 87t tetraenes must satisfy certain requirements concerning geometry in order to be able to participate in an [8 + 2] cycloaddition. For example, tetraenes 518 and 519 can undergo an [8 + 2] cycloaddition, whereas an [8 + 2] cycloaddition with 520 is virtually impossible. Due to its fixed -system, 519 is more reactive in cycloaddition reactions than 518 and is therefore more often encountered in the literature. [8 + 2] Cycloadditions have been applied only... 

Intramolecular Diels—Alder reactions without prior 1,4-addition of oxygen (cf. previous section) have similarly been postulated for a number of [2.2]paracyclophane analogs. When [2](2,5)furano[2](l,4)naphthalen-ophane (42) is heated in excess dimethyl acetylenedicarboxylate at 100 °C, a polycyclic compound of structure 134 is formed. The mechanism of formation of 134 is most probably as follows 101> the furan moiety reacts as active diene component in an intermolecular Diels—Alder reaction to give 135. This is followed by further intramolecular 1,4-addition with the unsubstituted naphthalene ring as diene component to give the product 133, which has been isolated. 

Industrially this diene is made the same way as ethylidenenorbomene from butadiene and ethene, but now isomerisation to 2,4-hexadiene should be prevented as the polymerisation should concern the terminal alkene only. In both systems nickel or titanium hydride species react with the more reactive diene first, then undergo ethene insertion followed by (3-hydride elimination. Both diene products are useful as the diene component in EPDM rubbers (ethene, propene, diene). The nickel hydride chemistry with butadiene represents one of the early examples of organometallic reactions studied in great detail [22] (Figure 9.14). 

Naturally, the question arises as to whether the diene component really has to be in its i -cis form for the cation-radical Diels-Alder reaction. According to calculations by Hofmann and Schaefer 1999, the i-trani-butadiene is more stable than its s-cis, isomer by 12 kJ moE, and for the cation-radicals, the trans preference is even somewhat pronounced (16 kJ moE )-... 

The non-aromatic nature of the pyran-2-one ring is evident in its behaviour as the diene component in Diels-Alder cycloadditions. With dimethyl acetylenedicarboxylate (DMAD, dimethyl but-2-ynedicarboxy-late), for example, it gives an adduct that spontaneously eliminates carbon dioxide to yield dimethyl phthalate (dimethyl benzene-1,2-dicarboxylate) (Scheme 4.7)... 

Furan can act as a diene in cydoaddilion reactions, but pyrrole only does so when activated by A-substilulion with an electron-withdrawing group. Thiophene I, I-dioxide is also an effective diene component in [4 + 2] cycloadditioiis. 

Among the most intensively investigated of all the chalcone Diels Alder adducts are a group obtained solely from Morus species in which the diene component of the reaction is a dehydroprenylflavanone. The structures of several such compounds published prior to 1992 have now been revised on the basis of new spectroscopic and chemical data. Among the most important of the techniques used were two-dimensional NMR and circular dichroism spectroscopy. The revised structures listed in Table 16.5 are those of sanggenons C (210), D (211), E (212), and O (213). In these compounds, the flavanones show the common feature... 

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