Radical coupling alcohols

The reaction of BA with isopropyl alcohol is particularly revealing. Direct irradiation of DABA in neat isopropyl alcohol gives the ether (17%) expected from the reaction of the singlet carbene, and the radical coupling products characteristic of the triplet spin state (21). The ratio of the yields of radical-derived products to ether depends inversely on the concentration of isopropyl alcohol in a benzene solution. This behavior is particularly meaningful when compared with that of FL, XA and DPM. For these... 

The propargylic alcohol 102, prepared by condensation between 100 and the lithium acetylide 101, was efficiently reduced to the hydrocarbon 103, which on treatment with potassium tert-butoxide was isomerized to the benzannulated enyne-allene 104 (Scheme 20.22) [62], At room temperature, the formation of 104 was detected. In refluxing toluene, the Schmittel cyclization occurs readily to generate the biradical 105, which then undergoes intramolecular radical-radical coupling to give 106 and, after a prototropic rearrangement, the llJ-f-benzo[fo]fluorene 107. Several other HJ-f-benzo[fo]fluorenes were likewise synthesized from cyclic aromatic ketones. 

Treatment of the propargylic alcohol 144, readily prepared from condensation between benzophenone (143) and the lithium acetylide 101, with thionyl chloride promoted a sequence of reactions with an initial formation of the chlorosulfite 145 followed by an SNi reaction to produce in situ the chlorinated and the benzannulated enyne-allene 146 (Scheme 20.30) [62], A spontaneous Schmittel cyclization then generated the biradical 147, which in turn underwent a radical-radical coupling to form the formal [4+ 2]-cycloaddition product 148 and subsequently, after a prototropic rearrangement, 149. The chloride 149 is prone to hydrolysis to give the corresponding 11 H-bcnzo h fluoren-ll-ol 150 in 85% overall yield from 144. Several other llff-benzo[fc]fluoren-ll-ols were likewise synthesized from benzophenone derivatives. 

Attachment of Hydroxycinnamic Acids to Structural Cell Wall Polymers. Peroxidase mediation may also result in binding the hydroxycinnamic acids to the plant cell wall polymers (66,67). For example, it was reported that peroxidases isolated from the cell walls of Pinus elliottii catalyze the formation of alkali-stable linkages between [2-14C] ferulic acid 1 and pine cell walls (66). Presumably this is a consequence of free-radical coupling of the phenoxy radical species (from ferulic acid 1) with other free-radical moieties on the lignin polymer. There is some additional indirect support for this hypothesis, since we have established that E-ferulic acid 1 is a good substrate for horseradish peroxidase with an apparent Km (77 /tM), which is approximately one fifth of that for E-coniferyl alcohol (400 /iM) (unpublished data). 

Aromatic Ring Cleavage of Phenolic 0-0-4 Substructure Model Compounds by Laccase. When vanillyl alcohol was used as a substrate, only biphenyl formation (C5-C5 linked) occurred and no evidence for the formation of any ring-opened products was obtained (26). Hence, we also examined the effect of laccase on the sterically hindered 4,6-di-<-butylguaiacol substrate 50, as it would be unlikely to undergo such free-radical coupling reactions... 

Not all of these reactions can be fitted to a single simple reaction scheme. It is apparent that in cyclohexene and in isopropyl alcohol at room temperature the first step is hydrogen abstraction from the solvent followed by radical coupling. Most of the major products from the reaction in cyclohexane can be accounted for by a reaction scheme similar to that invoked to account for the products observed from the irradiation of biacetyl and benzil in cyclo-... 

Fraser-Reid s stereocontrolled synthesis of the Woodward reserpine precursor 195 relied upon a tandem 5-exol6-exo radical cyclization of pyranose-derived dienes [76-77]. As outlined in Scheme 36, a,P-unsaturated ester 188 was prepared by free radical coupling of iodide 187 with a tin acrylate. After hydrolysis of 188 (MeONa, MeOH, 100%) to give primary alcohol 189, the silicon tethered diene 190 was installed by silylation. Treatment of 190 with n-BujSnH led to the desired cage molecule 192 in high yield via a 5-exo-trig cyclization to intermediate 191 followed by a 6-exo cyclization. Tamao oxidation of tricycle 192 led to diol... 

Termination of the autoxidation chain process occurs as peroxyl radicals couple to yield non-radical products. This reaction takes place through an unstable tetroxide intermediate. Primary and secondary tetroxides decompose rapidly by the Russell termination mechanism to yield three non-radical products via a six-membered cyclic transition state (Fig. 95). The decomposition yields the corresponding alcohol, carbonyl compound, and molecular oxygen (often in the higher energy singlet oxygen state) three... 

As mentioned in Sec. 15.2.2, hydrogen abstraction of benzylic hydrogens by the /77i triplet state of ketones is generally efficient and offers an access to benzylic radicals. However, the method is rarely of preparative interest since benzylic and ketyl radicals couple statistically giving a mixture of bibenzyls, alcohols, and pinacols, although the initial hydrogen abstraction may show some interesting intramolecular selectivity with polymethylbenzenes and substituted alkylbenzenes [220,221]. However, in... 

Tetrahydrofurans can be synthesized by intramolecular substitution reactions. y-Bromo or iodo alcohols are common starting materials that readily cyclize under basic conditions. Tetrahydrofuran derivative 3 is obtained after radical coupling of iodide 1 with pent-4-en-l-ol... 

In 1960 s, CIDEP was less popular than CIDNP because CIDEP did need much faster measuring techniques than CIDNP. This is due to much faster relaxation times (usually less than 1 /r s) of polarised electron spins than those (usually a few second for protons) of nuclear spins. In 1968, Smaller et al. [2] observed a population inversion for the cyclopentyl radical with a 2-MHz ESR apparatus coupled with a 15 MeV electron beam with pulse duration of 0.5 -4.0 /z s. The response time of the system corresponded to a time constant of 1.6/z s. In 1970, Atkins et al. [3] obtained the photo-CIDEP for the ketyl radical from benzophenone in paraffin solvents with a 2-MHz ESR apparatus coupled with a 20-ns laser flash. Under favorable chemical conditions, Wong and Wan [4] demonstrated that the photo-CIDEP for some semiquinone radicals in alcohol solvents could be observed with a commercial ESR spectrometer having a 100-kHz modulation unit and a custom-designed rotating sector giving light pulses. 

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