1.Labeled oxazaphosphorines for applications in mass spectrometry studies. 2. Synthesis of
deuterium-labeled 2-dechloroethylcyclo-phosphamides and 2- and 3-dechloroethylifosfamides
James B. Springer, O. Michael Colvin, Susan M. Ludeman*. J. Label Compd. Radiopharm 2014, 57, 110-114
As reported, 3-hydroxypropionitrile was reacted with NaOD/D2O(≥98 atom %D) to give [2,2-2H2]-3-deuterioxypropionitrile (DOCH2CD2CN) in 65% yield [Rf 0.52, EtOAc-hexanes (3:1)]. This nitrile was then reduced with LiAlD4 (98 atom %D) according to the literature to give the ﬁna product [96% yield].
With minor modiﬁcation to a literature preparation of unlabeled material, AlD3 [from LiAlD4 (98 atom %D, 1.0 g 22.6 mmol)] was reacted with [2,2,3,3-2H4]-7 (1.5 g 6.4 mmol) for ~12 h. The flask was then cooled (ice bath), and the reaction was quenched with the dropwise addition of 1M sodium potassium tartrate (5.0 mL). The mixture was diluted with water (100 mL) and CH2Cl2 (50 mL); 40% NaOH (~1.0–1.5 mL) was added to insure a basic pH. The phases were separated, and the aqueous layer was extracted with CH2Cl2 (3 × 50 mL). All organic layers were combined dried (Na2SO4), ﬁltered, and evaporated to afford the product (86%) as a pure, colorless oil [Rf 0.50 in NH3-saturated CH3OH : CH2Cl2 (1:9)].
2. Sequential Electron-Transfer and Proton-Transfer Pathways in Hydride-Transfer Reactions from Dihydronicotinamide Adenine Dinucleotide Analogues to Non-heme Oxoiron(IV) Complexes and p-Chloranil. Detection of Radical Cations of NADH Analogues in Acid-Promoted Hydride-Transfer Reactions
Shunichi Fukuzumi*, Hiroaki Kotani, Yong-Min Lee, Wonwoo Nam*. J. AM. CHEM. SOC. 2008, 130, 15134-15142
Acetonitrile (MeCN) and ether were dried according to the literature procedures and distilled under Ar prior to use. Iodosylbenzene (PhIO) was prepared by a literature method. Non-heme iron(II) complexes, Fe(TMC)(CF3SO3)2, Fe(N4Py)(CF3SO3)2, and Fe(Bn-TPEN)(CF3SO3)2, and their oxo-iron(IV) complexes, [(TMC)FeIV (O)] 2+, [(N4Py)FeIV (O)] 2+, and [(Bn-TPEN)FeIV (O)]2+, werepreparedbythe literaturemethods. For example, [(TMC)FeIV (O)] 2+ was prepared by reacting Fe(TMC)(CF3SO3)2 (0.5 mM) with 1.2 equiv of PhIO (0.6 mM) in CH3CN at ambient temperature. 10-Methyl-9,10-dihydroacridine (AcrH2) was prepared from 10-methylacridinium iodide (AcrH+I-) by reduction with NaBH4 in methanol and puriﬁed by recrystallization from ethanol. AcrH+I- was prepared by the reaction of acridine with MeI in acetone, converted to the perchlorate salt (AcrH+ClO4-) by the addition of magnesium perchlorate to AcrH+I- , and puriﬁed by recrystallization from methanol. The dideuterated compound,[9,9’-2H2]-10-methylacridine (AcrD2), was prepared from 10-methy-lacridone by reduction with LiAlD4 in ether. 9-Substituted (9-alkyl or 9-phenyl) 10-methyl-9,10-dihydroacridine (AcrHR; R Me, Et, and Ph) was prepared by the reduction of AcrH I with the corresponding Grignard reagents (RMgX). AcrDPh was prepared by reducing Acr Ph with NaBD4 and puriﬁed by recrystallization from ethanol. 9-Substituted 10-methylacridinium perchlorate (AcrR ClO4; R Me, Et, and Ph) was prepared by the reaction of 10-methylacridone in dichloromethane with the corresponding Grignard reagents (RMgX) and puriﬁed by recrystallization from ethanol diethyl ether. The dideuterated compound, 1-benzyl-1,4-dihydro[4,4’-2H2]nicotinamide (BNAH-4,4’-d2), was prepared from monodeuterated
compound (BNAH-4-d1) by three cycles of oxidation with p-chloranil in dimethylformamide and reduction with dithionite in deuterium oxide.