2-deuterio-4-phenyl

The catalytic cycle was established by the outcome of these deuterium labeling studies. Thus, after transmetallation from boron to give the phenylrhodium species, the alkyne inserts into the phenyl-rhodium bond to form the alkenylrhodium intermediate (Scheme 4.29). It follows that rhodium moved from the vinylic position of the alkenylrhodium intermediate to the ortho position of the phenyl ring [42]. The so-formed 2-(alkenyl)phenylrhodium intermediate then undergoes hydrolysis with D2O to give the deuterio phenylation product and the active hydroxorhodium intermediate. 

Phenyl-2-(4-nitro-phenyl)-2-deuterio propansdure- met hy tester1... 

TITANOCENE-CATALYZED SYNTHESIS OF METHYL 4-DEUTERIO-4-PHENYL-4-HYDROXYBUTANOATE... 

Optically active olefin (Z)-(S)-( )-l-deuterio-3,4-dimethyl-l-phenyl-2-pentene, 1 (Scheme 3), was photo-oxidized in acetone at 10°C. The tertiary al-lylic hydroperoxide was obtained in high yield and only in the trans configuration. 

The favored formation of acetylated l-a-deuterio-l,5-anhydro-D-glucitol 78 in labeling experiments has been put forward to support the occurrence of carbohydrate radicals as intermediates in the photolytic decomposition of glucopyranosyl phenyl sulfone acetates104 as well as the Cp2TiBD4193 and zinc-silver/graphite-197 mediated reduction of glycosyl halides. Cationic intermediates would have favored the opposite stereochemistry 26... 

Caproic acid, as glycogenic agent, II, 134 labelled with isotopic C, III, 231 —, deuterio-, metabolism of, II, 152 Caprylic acid, as glycogenic agent, II, 134 labelled with isotopic C, III, 231 metabolism of, II, 152 Carbamic acid, N-phenyl. See Carba-nilic acid. 

The reactions of ( )-l-deuterio- and ( )-2-deuterio-l-decenyl(phenyl)iodonium tetrafluoroborates with TB AC1 in dichloromethane have also been investigated (equations 207 and 208)146. The deuterium content of the alkyne, or lack thereof, and the effect of the /Pdeuterium atom on the chlorodecene/decyne ratio are consistent with alkyne production primarily via a cis / -elimination process. 

Once again (cf equation 205), the behavior of tetrabutylammonium fluoride (TBAF) is exceptional. Thus, the treatment of (E)-1 -decenyl(phenyl)iodonium tetrafluoroborate with ten equivalents of TBAF in acetonitrile leads exclusively to 1-decyne (equation 212)146. Furthermore, the reactions of the a- and /1-deuterio isotopomers of the decenyliodonium salt with one equivalent of TBAF in dichloromethane are clearly consistent with alkyne formation via the a-elimination-alkylidenecarbene pathway (equations 213 and 214)146. 

Although alkyne formation from / ,/ -disubstituted vinyliodonium salts via the a-elimination-alkylidenecarbene pathway is expected, the generation of 1-decyne from ( )-l-decenyl(phenyl)iodonium fluoroborate (equation 230) might also occur via syn -elimination. That a-elimination is dominant, even in this case, has been demonstrated by treatment of the a- and / -deuterio-l-decenyl isotopomers with triethylamine (equations 233 and 234)128. 

For example, irradiation of ( )-iV-isopropyl-5-phenyl-4-pentenamine (0.01 M in acetonitrile purged with nitrogen) in a Rayonet reactor fitted with RPR 3000 lamps for 15 minutes (>95% conversion) results in the formation of A -isopropy 1-2-phenyl piperidine (65% yield) and 5-phenyl-4-pentenal (15%), whereas irradiation of the A-Zert-butyl compound resulted in quantitative formation of the imine28. cis Selective N-D addition was observed in the cyclization of (ZO-Af-deuterio-Af-methyl-S-phenyl-d-pentenamine [( )-l], but from the (Z)-isomer [(Z)-l] the cis/trans ratio was 3 1 28,66, since rotational equilibration of the biradical intermediate is faster than cyclization. 

Bis-[4-methoxy-phenyl]-2-cyclopropenyliden)-9-(dicyano-methylen)-9,10-dihydro- 2975 2(or 3)-Chloromethyl- 2879 lO-Deuterio-9-methoxycarbonyl- 2880 1 -Hy droxy-7-methoxy-1 -(1 -phenylthio-cy clo-propyl)-l,2,3,4-tetrahydro- 1480 9-Melhoxycarbonyl- 2888 7-Methoxy-l-(l-phenylthio-cyclopropyl)-3,4-dihydro- 1480 9-Methyl- 2048... 

Aryl- und alkyl-substituierte Thiophene werden im wesentliclien isomerisiert4 (2,3-Verschiebung), wobei 3-Phenyl-thiophene mit zusatzlieh Phenyl-, Deuterio- und Methyl-Substituontcn cine besondere Spezifitat zeigen ... 

Ar — CgDsi R1 —D 5-Deuterio- 4-Deuterio-3-pentadeutei io phenyl-thiopken... 

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