The mechanism of the norrish type II reaction of α-keto-acids and esters

Methyl-α-keto-octanoate undergoes a Type II reaction to give pent-1-ene and photophysical measurements show that this and the Type II reactions of α-keto-acids occur, contrary to previous claims, from the excited singlet state.     

Reactivity differences between dimorphs in a crystalline phase norrish type II reaction

The dimorphs of α-adamantyl-p-chloroacetophenone (P2₁/n and C2/c) undergo solid state Norrish type II cyclobutanol formation with different stereoselectivity. Based on the X-ray crystal structure data, it is concluded that conformational factors rather than packing differences control the photoproduct stereochemistry.     

Intramolecular photocycloaddition of cyclic thioimides as a method for heterocyclic synthesis

Cyclic thioimides undergo photocycloaddition with tethered pi-bonds in a regiospecific manner to afford spirocyclic amidothietanes. These highly strained multicycles undergo a subsequent ring opening reaction to furnish novel fused pyrrolizinones.     

Photochemistry of macrocyclic ketones within zeolites: competition between norrish type I and type II reactivity

Photolysis of macrocyclic mono- and diketones (1 and 2) included in X and Y zeolites gives Norrish type I products in addition to the products obtained via the Norrish type II process, the only observed process in isotropic media. Enhancement of the type I over the type II process is cation-dependent and especially large enhancements are obtained with Li and Na as cations. The zeolite effect is attributed to a reduction in the rate of the Norrish type II -hydrogen abstraction process.     

Computer-assisted site-specific functionalization in the gibberellin series; norrish type II photocyclization via a 9-membered transition state

The site-specific Norrish II type reaction of the gibberellin oxo ester , prepared in two steps from tetraacetyl- GA₃, anhydride , to the photolactone , is reported. By potential energy calculations based on the X-ray analysis of , it is shown that the regio- and stereoselectivity of the photocyclization can be predicted involving a 9-membered cyclic transition state in the H-abstraction step. The structure of the photolactone was determined by spectroscopic data, especially NOE measurements.     

13C CIDNP derived from a 1,4-biradical generated in a norrish type II photolysis

NorRIsh type II photolysis of 1-benzoyl-1-methylcyclopentane, labeled with ¹³C in the carbonyl position, produces emissive CIDNP in the cyclization product. The polarization is consistent with the formation of a 1,4-biradical with a singlet ground state. By comparing this result with those for other biradicals, inferences are drawn about possible factors governing the singlet—triplet splittings of biradicals.     

Palladium-catalyzed cross-coupling reaction of alkynylzincs with benzylic electrophiles

The reaction of alkynylzinc bromides with benzyl bromides or chlorides in the presence of a catalytic amount of Pd(DPEphos)Cl₂ in THF at 23 °C cleanly produces the corresponding benzylated alkynes in 73-97% yields. With 10⁻³ mol % of Pd(DPEphos)Cl₂, the maximum turnover number of 7.1 × 10⁴ has been observed for the formation of PhCCCH₂Ph.     

Synthesis of benzylic boronates via palladium-catalyzed cross-coupling reaction of bis(pinacolato)diboron with benzylic halides

The palladium cross-coupling reaction of benzyl halides with diboron 1 yielded structurally diverse pinacol benzylic boronates. Under these reaction conditions, sensitive functionalities such as esters and nitriles are tolerated and the benzylic boronates are obtained in good to high yields.     

The knoevenagel reaction of malononitrile with some cyclic β-keto-esters—II: Mechanism of formation of heterocyclic reaction products

The formation of alkoxypyridinols 3a and 3b from the Knoevenagel reaction products 2a and 2b was shown to proceed by a mechanism in which the ester CO group initiates ring closure by intramolecular nucleophilic attack on the cyano group, possibly assisted by an acidic catalyst. Opening of the oxygen ring after nucleophilic attack by a basic catalyst on the former ester carbonyl C atom results in the formation of an amide, which in turn affords the alkoxypyridinols by a conventional cyclization mechanism.     

Benzyl radical addition reaction through the homolytic cleavage of a benzylic C-H bond

Direct generation of a benzyl radical by C-H bond activation of toluenes and the addition reaction of the resulting radical to an electron deficient olefin were developed. The reaction of dimethyl fumarate with toluene in the presence of Et(3)B as a radical initiator at reflux afforded 2-benzylsuccinic acid dimethyl ester in good yield.     

Murexide reaction of caffeine with hydrogen peroxide and hydrochloric acid. II

In continuation of the study on the murexide reaction of caffeine with 3% hydrogen peroxide/hydrochloric acid and then with ammonia giving a purple coloration, we investigated the oxidation reaction of caffeine with 6% hydrogen peroxide/hydrochloric acid to isolate ten reaction products, 3-hydroxy-4,6-dimethyloxazolo[4,5-d]pyrimidine-2,5,7(3H,4H,6H)-trione 1 , 1,3-dimethylalloxan 2 , murexoin 3 , 1,3,7-trimethyl-2,6,8-trioxo-9-hydroxy-1H,3H,7H-xanthine 5 , 1,3,7-trimethyl-2,6,8-trioxo-1H,3H,7H-xanthine 6 , 1,3,7-trimethyl-2,6-dioxo-8-chloro-1H,3H,7H-xanthine 7, 5-(1,3-dimethyl-1,2,3,4,5,6-hexahydro-2,4,6-trioxopyrimidin-5-yl)-aminomethylene-1,3-dimethyl-1,2,3,4,5,6-hexahydro-2,4,6-trioxopyrimidine ammonium salt 9 , 1,3-dimethylpalabanic acid 10 , 1-methyl-2,4,5-trioxoimidazole 11 , 3-hydroxy-5,7-dimethyloxazolo[5,4-d]pyrimidine-2,4,6(3H,5H,7H)-trione 12 and 4,6,8-trimethyl-1,2,4-dioxazino[6,5-d]pyrimidine-3,5,7(4H,6H,8H)-trione 13 . The oxidation reaction using 6% hydrogen peroxide/hydrochloric acid was found to produce a similar purple coloration to that of the murexide reaction despite no subsequent addition of ammonia, indicating the liberation of ammonia by the oxidation of caffeine. Among the above compounds, the purple colored substance murexoin 3 and the yellow colored compound 9 were both ammonium salts, and compound 5 was the red colored substance. In the present investigation, these three compounds were found to contribute to the coloration.     

Fe(II)-catalyzed N-alkylation of sulfonamides with benzylic alcohols

The FeCl₂/K₂CO₃ catalyst system was developed successfully for the N-alkylation of sulfonamides with benzylic alcohols via borrowing hydrogen method. XPS analysis suggested a possible catalyst cycle between Fe(II) and Fe(0). Under the optimized condition, the scope of the protocol was demonstrated in 21 different alkylation reactions. High yields, in general >90%, are achieved in most cases.     

Copper(II) catalyzed cross-dehydrogenative coupling of cyclic benzylic ethers with simple carbonyl compounds by Na2S2O8

Copper(II) catalyzed cross-dehydrogenative coupling of cyclic benzylic ethers with a variety of simple carbonyl compounds mediated by Na₂S₂O₈ is developed. The scope of carbonyl components is broad, including simple aldehydes as well as ketones. The use of Na₂S₂O₈ as the oxidant for the CDC reaction is attractive based on economical and environmental factors.