Olefins crowded

This extremely air-sensitive compound, which is valence isoelectronic to an olefin, has been structurally characterized by X-ray diffraction. It has a short carbon-phosphorus double bond (1.62 A) the phosphorus and carbon atoms adopt a trigonal planar geometry with a dihedral angle of 60° (Fig. 3). This value is significantly larger than that reported for the most crowded olefin.61 Formally, this compound can be viewed as the product of a car-bene-carbenoid coupling between bis(trimethylsilyl)carbene and bis(diiso-propylamino)phosphenium triflate. Note that another route to methylene-phosphonium salt has been reported by Griitzmacher et al.62... 

Photooxetane formation is quite inefficient, a fact which usually points to the presence of an intermediate which can partially revert to ground state reactants. Cleavage of the diradical must be responsible for some of the inefficiency in oxetane formation 129>. However, in the past few years convincing evidence has appeared that a CT complex precedes the diradical iso.isi). The two most telling pieces of evidence are the relative reactivities of different alkenes 130> and the absence of any measurable secondary deuterium isotope effect on quenching rate constants 131>. Relative quenching rates of sterically un crowded olefins are proportional both to the ionization potentials of the donor olefins 130> and to the reduction potentials of the acceptor ketones 131>, as would be expected for a CT process. Inasmuch as n,n triplets resemble electron-deficient alkoxy radicals, such substituent effects would also be expected on direct radical addition of triplet ketone to olefin. However, radical addition would yield an inverse isotope effect (in, say, 2-butene-2,3-d2) and would be faster to 1,1-dialkylethylenes than to 1,2-dialkylethylenes, in contrast to the actual observations. 

Crowded Olefins. Force field calculations have mainly been used for exploring structural details of olefins with bulky substituents. The parameters of the CFF, SFF, MM1, and MM2 force fields have been adjusted to reproduce the geometry of several crowded olefins with errors in bond angles less than 2.0° and in lengths of the double bond less than 0.1 pm (62,64,66). 

An optically active and sterically crowded olefin 84, with similar structural features, has been prepared from ( + )camphor (105). Other methods, which have been used for the generation of distorted olefins, are illustrated in the following examples. Heating di-terf-butylneopentylcarbinyl-p-nitrobenzoate (85) gave tri-terf-butylethene (66) in 30% yield (106). 

The ultraviolet spectra of a series of substituted ethylenes and sterically crowded olefins have been determined (Table 15). 

The ultraviolet spectra of crowded olefins and substituted butadienes have been studied the sign of the Cotton effect has been related to the chirality of a series of w-molecular complexes of olefins with tetracyanoethylene the sign of the chiral-optical effects of non-planar heteroannular cisoid dienes is opposite to that predicted from the diene rule. Studies of linear and circular dichroism in mono-olefins and magnetic circular dichroism of conjugated olefins have been made, and the experimental ionization potentials of fourteen alkenes have been correlated with the inductive effects of substituents. ... 

Lenoir and his co-workers have published further syntheses of sterically crowded olefins. Many hindered ketones, l-ethyladamantan-2-one (6) for... 

CM with the Hindered Olefin 1,1-Disubstituted and trisub stituted olefins do not usually dimerize even in the presence of [Ru]-II, and these olefins are categorized as type Iff or type fV. The sterically crowded olefin such as 2-methyl-2-butene, however, was found to be available as a CM partner by Grubbs and co-workers. Porco and Qi employed this CM partner for the synthesis of clusianone 105, which is a potential anti-HIV therapeutic agent isolated from the floral resin of clusia species (Scheme 24.25). The isopropenyl moiety was smoothly incorporated into the side chain of clusianone precursor 104 by CM reaction of 102 with 103 as a solvent. 

The Corey-Winter reaction provides a useful method for the preparation of olefins that are not accessible by other routes. For instance it may be used for the synthesis of sterically crowded targets, since the initial attack of phosphorus at the sulfur takes place quite distantly from sterically demanding groups that might be present in the substrate molecule. Moreover the required vicinal diols are easily accessible, e.g. by the carbon-carbon bond forming acyloin ester condensation followed by a reductive step. By such a route the twistene 10 has been synthesized ... 

The dihalogen complexes with olefin donors were first identified spectroscopically in the mid-1960s [42-45] and extensive experimental and computational studies have been carried out by Chiappe, Lenoir and coworkers in recent years [46 - 48 ]. These systems are highly unstable, since the complexation of dihalogens with olefins is followed rapidly by the formation of ionic intermediates and further chemical transformations. Therefore, attention in the corresponding work has mostly focused on hindered olefins, although the spectral characteristics of complexes with less sterically crowded and alkyl- as well as chloro-substituted and cyclic olefins are also reported [44]. The absorption maxima for the dihalogen complexes with olefins (evaluated by the subtraction... 

For cyclopropanations with ethyl diazoacetate, a rather weak influence of the olefin structure has been noted 59 60, (Table 7). The preference for the sterically less crowded cyclopropane is more marked for 1,2-disubstituted than for 1,1-disubstituted olefins. The influence of steric factors becomes obvious from the fact that the ratio Z-36/E-36, obtained upon cyclopropanation of silyl enol ethers 35, parallels Knorr s 90> empirical substituent parameter A.d of the group R 60). These ZjE ratios, however, do not represent the thermodynamic equilibrium of both diastereomers. 

For example, substituents in terminal olefins (43) in the resulting nitronates (35) are generally adjacent to the C-6 atom. The alkoxy and siloxy substituents from vinyl ethers and silyl enolates respectively, as well as the amino group from enamines, are oriented in the same positions. In the case of tris-substituted olefins, C-6 is the most crowded atom in the resulting nitronates. 

The coordinated ethylene is readily expelled at 25 °C by the attack of a conjugated diene and the hydride is transferred to the sterically less crowded diene terminus. Thus the niobium hydrido-olefin complexes serve as convenient reagents for the preparation of 1,2- or 1,3-dialkyl-substituted allylniobium compounds starting from butadiene, (E,E) and (/i,Z)-2,4-hcxadicnc, (E)- and (Z)-l,3-pentadiene (equation 1), 3-methyl-l,3-pentadiene and isoprene (equation 2). All the allyl niobium compounds synthesized were isolated as air-sensitive pale-yellow crystals by crystallization from hexane. 

This process seems much simpler than the Ziegler process, and you may wonder why it has not crowded Ziegler out. The problem is the olefin feed. Where do you get a ready supply of olefins the right size to feed to the process The answer is you have to malce them, and therein lies the rub. Normal paraffins from petroleum waxes or other chemical processes provide the feedstock to a two-step process, chlorination and dehydrochlorination, which produces an olefin corresponding to the paraffin. 

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