Electron rich olefins

The other important direct alkylation processes involve reaction of electron-rich olefinic compounds with either tin metal or stannous chloride (tin(II) chloride) in the presence of stoichiometric amounts of hydrogen chloride (22). Butyl acrylate (R = C Hg) was used commercially in this process to prepare the estertin or P-carboalkoxyethyltin chlorides as iHustrated in the foUowing. 

Dioxetanes are obtained from an a-halohydroperoxide by treatment with base (41), or reaction of singlet oxygen with an electron-rich olefin such as tetraethoxyethylene or 10,10 -dimethyl-9,9 -biacridan [23663-77-6] (16) (25,42). 

Classical chemiluminescence from lucigenin (20) is obtained from its reaction with hydrogen peroxide in water at a pH of about 10 Qc is reported to be about 0.5% based on lucigenin, but 1.6% based on the product A/-methylacridone which is formed in low yield (46). Lucigenin dioxetane (17) has been prepared by singlet oxygen addition to an electron-rich olefin (16) at low temperature (47). Thermal decomposition of (17) gives of 1.6% (47). 

The initial bond formation between the -> ir excited carbonyl compound and an alkene can occur by interaction of the half-filled n -orbital of the [I CO] with the ir-system of the alkene, in a sense transferring a tt-electron to the -orbital and making a bond between an alkene carbon and the carbonyl oxygen. In this process (common for electron rich olefins) the plane formed by the alkene carbons and their four substituents is perpendicular to the plane of the carbonyl groups and its two substituents (Figure 1). In the... 

Reaction of triethylsilyl hydrotrfoxide with electron-rich olefins to gh/e dioxetanes that react IntrarTMlecularly with a keto group in the presence of t-txrtyidimethyl silyl triflateto afford 1,2,4 Inoxanes also oxydatnre cleavage ol alkenes Also used in cleavage ol olefins... 

The pyrolysis of sodium chlorodinuoroacetate is still a widely used, classical method for generating difluorocarbene, especially with enol and allyl acetates [48, 49, 50, 51] (equation 21) A convenient alternative that avoids the hygroscopic salt uses methyl chlorodifluoroacetate with 2 equivalents of a lithium chlonde-hexa-methylphosphoric triamide complex at 75-80 °C in triglyme [52], Yields are excellent with electron-rich olefins but are less satisfactory with moderately nucleophilic alkenes (4-5% yields for 2-bulenes)... 

Dienamines undergo 1,4 cycloaddition with sulfenes as well as 1,2 cycloaddition. For example, l-(N,N-diethylamino)butadiene (111), when treated with sulfene (generated from methanesulfonyl chloride and triethyl-amine), produces 1,4 cycloadduct 116 in an 18 % yield and di-1,2-cycloadduct 117 in a 60 % yield (160). Cycloadduct 116 was shown not to be the precursor for 117 by treating 116 with excess sulfene and recovering the starting material unchanged (160). This reaction probably takes place by way of zwitterion 115, which can close in either a 1,4 or 3,4 manner to form cycloadducts 116 and 118, respectively. The 3,4 cycloaddition would then be followed by a 1,2 cycloaddition of a second mole of sulfene to form 117. Cycloadduct 117 must form in the 3,4 cycloaddition followed by a 1,2-cycloaddition sequence rather than the reverse sequence since sulfenes undergo cycloaddition only in the presence of an electron-rich olefinic center (159). Such a center is present as an enamine in 118, but it is not present in 119. 

With this foundation, Boger communicated the use of 1,2,4-triazines as a dependable, azadiene equivalent for Diels-Alder approaches to substituted pyridines. Electron rich olefin 19, prepared from the corresponding ketone, was allowed to... 

Concerning nomenclature, fulvalene 2 and its related systems 1 and 3-6 are the parent structures of this class of heterocyclic cross-conjugated compounds. Both ring systems are numbered as shown in formula 9 (1,4,5,8-tetraazafulva-lene) beginning at the heteroatoms. Alternatively, as in the case of heptafulva-lene 10 (3,3 -diazaheptafulvalene), the numbers 1-7 and l -7 can be used.Tlie use of the name of the parent heterocycle connected by an olefinic double bond is often favored for the nomenclature of electron-rich olefines, for example, bis[3-(2,6-diisopropylphenyl)-4,5-dimethylthiazol-2-ylidene] for compound 51a (97LAR365). Similarly, azafulvalenes of type 11 and 12 can be re-... 

A considerable number of dihetero-diazafulvalenes are well-known by the name electron-rich olefins. Tliey are associated with the problem of... 

A large number of DTDAFs ( electron-rich olefins ) described above are very efficient donors, e.g., for their application in organic conductors however they are highly sensitive to air. Studies aimed at the preparation of such compounds, especially the aliphatic ones, have so far met with only limited success. For example, a few alkyl-substituted DTDAF derivatives could be detected electrochemically, but an attempt to isolate one of these only led to oxidation products (91JA985). Similarly, an elec-... 

Depending on the electronic state of azafulvalene and the reaction conditions, simple nucleophiles such as amines or alcohols show a different behavior. Upon heating methanol reacted with azafulvalenes as electron-rich olefins by addition to the central double bond (64BSF2857 67LA155). Using the TAF 77 (Ar = Ph), the addition reaction in a neutral benzene-ethanol solution required several days to obtain a minor amount of 147, while the reaction proceeded rapidly in the presence of a catalytic amount of potassium hydroxide (79JOC1241). Tlie yellow-colored adduct 147 can be reconverted to the quinoid starting material by irradiation (Scheme 58). 

Recently, Narasaka and co-workers have found that Tnitroalkyl radicals are generated by oxidadon of nci-nitroanions vrith CAN, and they undergo the intermolecidar addidon to electron-rich olefins. For example, when oxidadon is carried out in the presence of silylenol ethers, fi-nitroketones are formed in good yield. fi-Nitroketones are readily converted into u vrith base ("see Secdon 7.3, as shovm in Eq. 5.43. 

As formal a, /i-unsaturated sulfones and sulfoxides, respectively, both thiirene dioxides (19) and thiirene oxides (18) should be capable, in principle, of undergoing cycloaddition reactions with either electron-rich olefins or serving as electrophilic dipolarophiles in 2 + 3 cycloadditions. The ultimate products in such cycloadditions are expected to be a consequence of rearrangements of the initially formed cycloadducts, and/or loss of sulfur dioxide (or sulfur monoxide) following the cycloaddition step, depending on the particular reaction conditions. The relative ease of the cycloaddition should provide some indication concerning the extent of the aromaticity in these systems2. 

As expected, 1 1 (2 + 2) cycloadducts are obtained in the reactions of thiete dioxides with some typical electron-rich olefins, e.g. enamines and ynamines, although this cycloaddition has not proven to be general190. 

Catalytic cyclopropanation of alkenes has been reported by the use of diazoalkanes and electron-rich olefins in the presence of catalytic amounts of pentacarbonyl(rj2-ris-cyclooctene)chromium [23a,b] (Scheme 6) and by treatment of conjugated ene-yne ketone derivatives with different alkyl- and donor-substituted alkenes in the presence of a catalytic amount of pentacarbon-ylchromium tetrahydrofuran complex [23c]. These [2S+1C] cycloaddition reactions catalysed by a Cr(0) complex proceed at room temperature and involve the formation of a non-heteroatom-stabilised carbene complex as intermediate. 

Very much more persistent radicals, with a half-life of up to a year, and with the structures [(Me3Si)2CH]3Sn- and [(MejSiljCHljRSn-(R = Pr , Bu , Me, Et, Bu, or cyclopentadienyl) have been prepared by the photolysis of [(Me3Si)2CH]2Sn(II), or by photolyzing a mixture of the appropriate halide [ Me3Si)2CH]2RSnX with an "electron rich olefin (299, 300). 

In the photooxygenation of electron-rich olefins with allylic hydrogen atoms, ene reactivity usually dominates [96]. Nevertheless, other reactions become the preferred reaction mode. Inagaki et al. [92] attributed the exclusive [2h-2] cycloaddition... 

Lappert was the first to report, in 1983, the synthesis of chiral rhodium(I) and cobalt(I) imidazolinylidene complexes by heating an enantiopure electron rich olefin 3 in the presence of a complex precursor (Scheme 1) [9]. 

To explain the stereochemistry of the photoaddition, Buchi proposed that the reaction of electron-rich olefins and excited ketone involves an interaction of the electron-deficient carbonyl lone-pair orbital with the electron-rich 7r-olefin orbitals to form a diradical intermediate which could subsequently close to give the observed products. Indeed, reaction to yield the most stable diradical intermediate usually does nicely rationalize the observed product distribution. Examples of this are as follows11005 ... 

Reactions of aromatic ketones with electron-rich olefins are in general nonstereospecific, as evidenced by the same product distribution being obtained from reaction with both cis- and Oww-2-butene<92> ... 

The addition of thioketones to olefins is very interesting indeed. Unsubstituted electron-rich olefins yield 1,4-dithianes as final products(112) ... 

For some organic compounds, such as phenols, aromatic amines, electron-rich olefins and dienes, alkyl sulfides, and eneamines, chemical oxidation is an important degradation process under environmental conditions. Most of these reactions depend on reactions with free-radicals already in solution and are usually modeled by pseudo-first-order kinetics ... 

PET reactions [2] can be considered as versatile methods for generating radical cations from electron-rich olefins and aromatic compounds [3], which then can undergo an intramolecular cationic cyclization. Niwa and coworkers [4] reported on a photochemical reaction of l,l-diphenyl-l, -alkadienes in the presence of phenanthrene (Phen) and 1,4-dicyanobenzene (DCNB) as sensitizer and electron acceptor to construct 5/6/6- and 6/6/6-fused ring systems with high stereoselectivity. 

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