Synthesis hydrogen abstraction

Heterocyclic sulphoxides 65 mass spectra of 130-132 Hexahydronaphthalenols, synthesis of 310 Hofmann elimination 953 HOMO energies 1048, 1049 Homolytic substitution 1109 intramolecular 846 Horner-Wittig reaction 333 Hot electrons 892, 893 HSAB theory 282, 549 Hydrides, as reducing agents 934-941, 959 Hydrogen abstraction, photochemical 874, 876, 877, 879, 880... 

The radicals derived by hydrogen abstraction from 1,3-dithianes and 1,3-oxathianes undergo intramolecular addition to ot,P-unsaturated esters and hence facilitate the synthesis of cycloalkanones <96T9713>. 

Scheme 3.62. Domino radical hydrogen abstraction-cyclization procedure in the synthesis towards Aspidosperma alkaloids.

Two types of addition to pyrimidine bases appear to exist. The first, the formation of pyrimidine photohydrates, has been the subject of a detailed review.251 Results suggest that two reactive species may be involved in the photohydration of 1,3-dimethyluracil.252 A recent example of this type of addition is to be found in 6-azacytosine (308) which forms a photohydration product (309) analogous to that found in cytosine.253 The second type of addition proceeds via radical intermediates and is illustrated by the addition of propan-2-ol to the trimethylcytosine 310 to give the alcohol 311 and the dihydro derivative 312.254 The same adduct is formed by a di-tert-butyl peroxide-initiated free radical reaction. Numerous other photoreactions involving the formation by hydrogen abstraction of hydroxyalkyl radicals and their subsequent addition to heterocycles have been reported. Systems studied include 3-aminopyrido[4,3-c]us-triazine,255 02,2 -anhydrouri-dine,256 and sym-triazolo[4,3-fe]pyridazine.257 The photoaddition of alcohols to purines is also a well-documented transformation. The stereospecific addition of methanol to the purine 313, for example, is an important step in the synthesis of coformycin.258 These reactions are frequently more... 

Norrish Type II photocyclizations have been employed in many instances in the synthesis of nitrogen heterocycles. Type II cyclizations are the result of an intramolecular hydrogen abstraction by an excited carbonyl group followed by cyclization of the resulting biradical. Hydrogen abstraction from the y-carbon atom is normally preferred. The introduction of a nitrogen atom... 

The synthesis of a new benzo[6]furan-containing cyclophane has been achieved by irradiation of the starting diketone 113 via a 6-hydrogen abstraction from the o-alkoxybenzophenone. X-ray analysis shows that the cyclophane has a well-defined rectangular cavity <00TL1393>. 

The synthesis of 9-diazofluorene 19 is easily accomplished from commercially available 9-fluorenonehydrazone (HgO, Et20 followed by KOH in EtOH yield = 98%) [72], Diazo compounds on photolytic decomposition tend to generate carbenes [73,74], Fluorenylidene, generated by the photolysis of 9-diazofluorene adds to olefins with negligible amounts of hydrogen abstraction [75,76]. Copper and its salts, however, have been shown to lead to... 

Radical chain hydrosilylation of alkenes using RsSiH, where R = alkyl and/ or phenyl, is not very useful in synthesis because the hydrogen abstraction step is slow under standard experimental conditions (cf. Section 3.1). These reactions proceed under drastic conditions (Reaction 5.9) [3], but can be promoted under milder conditions by the presence of catalytic amounts of a thiol [27]. Thus, the propagation steps in Scheme 5.1 are replaced by those reported in Scheme 5.4, where the thiol acts as the catalyst and the H transfer agent (see Iso Section 4.5). 

Hydrogen abstraction Asymmetric synthesis Chiral crystal... 

Hi. Lysine. Gamma radiolysis of aerated aqueous solution of lysine (94) has been shown, as inferred from iodometric measurements, to give rise to hydroperoxides in a similar yield to that observed for valine and leucine. However, attempts to isolate by HPLC the peroxidic derivatives using the post-column derivatization chemiluminescence detection approach were unsuccessful. This was assumed to be due to the instability of the lysine hydroperoxides under the conditions of HPLC analysis. Indirect evidence for the OH-mediated formation of hydroperoxides was provided by the isolation of four hydroxylated derivatives of lysine as 9-fluoromethyl chloroformate (FMOC) derivatives . Interestingly, NaBILj reduction of the irradiated lysine solutions before FMOC derivatization is accompanied by a notable increase in the yields of hydroxylysine isomers. Among the latter oxidized compounds, 3-hydroxy lysine was characterized by extensive H NMR and ESI-MS measurements whereas one diastereomer of 4-hydroxylysine and the two isomeric forms of 5-hydroxylysine were identified by comparison of their HPLC features as FMOC derivatives with those of authentic samples prepared by chemical synthesis. A reasonable mechanism for the formation of the four different hydroxylysines and, therefore, of related hydroperoxides 98-100, involves initial OH-mediated hydrogen abstraction followed by O2 addition to the carbon-centered radicals 95-97 thus formed and subsequent reduction of the resulting peroxyl radicals (equation 55). 

The synthesis of pyrrolidines by the free radical transformation of (V-chloroamines, the Hofmann-Loeffler-Freytag reaction, is of preparative significance. The key step is the formation of a radical cation which abstracts hydrogen intramolecularly to form a carbon-based radical (Scheme 21(a)). This species then abstracts chlorine from another TV-chloroamine (60JA1657, 50JA2118). The observed positional selectivity for hydrogen abstraction is a consequence of the preferred adoption of a six-membered transition state. A typical conversion achieved is indicated in Scheme 21(b). 

The UV irradiation of allyloxy-ketones and -aldehydes has led, by 5-hydrogen abstraction, to a useful high-yield synthesis of the 2-alkenyl-3-hydroxytetrahydrofurans (80CC657). This substitution pattern occurs in the natural mycotoxins citreoviridin and asteltoxin (Scheme 56). 

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