N,1-(15)N2]-2'-deoxyadenosines

[reaction: see text] An efficient route to deoxyadenosine derivatives labeled on both the amino group and nitrogen 1 is uncovered. First, 3',5'-di-O-acetyl-2'-deoxy-1-(2-nitrobenzenesulfonyl)inosine (2a) and only 1.1 equiv of (15)NH4Cl are used for labeling position 1 (1a) through the isolation of the open intermediate and its cyclization with DBU in anhydrous CH3CN. Inosine 1a is then converted to [N,1-(15)N2]-3',5'-di-O-acetyl-N6-benzoyl-2'-deoxyadenosine (5a, the precursor of 6a) via a Pd/dppf-catalyzed chloride-to-benzamide replacement, by using again only 1.1 equiv of the labeling source.     

Synthesis of 9-[(2-hydroxy-1-phosphonylethoxy)ethyl]guanine, 1-[(2-hydroxy-1-phosphonylethoxy)ethyl]cytosine and 9-[(2-hydroxy-1-phosphonylethoxy)ethyl] adenine

The acyclic nucleoside phosphonate analogues, 9-[(2-hydroxy-1-phosphonylethoxy)ethyl]guanine 6 , 1-[(2-hydroxy-1-phosphonylethoxy)ethyl]cytosine 7 and 9-[(2-hydroxy-1-phosphonylethoxy)ethyl]adenine 8 , have been prepared by the coupling of a tosylate of the phosphonate side chain 12 with a purine or pyrimidine base followed by deprotection of the blocking groups.     

Copper complexes of 1-[(2-carboxyethyl)benzene]-3-[2-pyridine]triazene

The triazenide, 1-[(2-carboxyethyl)benzene]-3-[2-pyridine]triazene (HL), has been synthesized. In the presence of Et₃N, the reaction of HL with Cu(OAc)₂·H₂O or CuCl₂·2H₂O gives the tetranuclear copper(II) complexes {Cu₄(L)₂(μ₂-OH)₂(OAc)₄} 1 and {Cu₄L₄(μ₄-O)Cl₂} 2, respectively. The X-ray crystal structures of both complexes have been obtained. Magnetic studies indicate significant antiferromagnetic coupling between the copper(II) centers for both complexes, with coupling constants (J) of −493.4 cm⁻¹ for 1 and −165 cm⁻¹ for 2.     

Synthesis of (Z)-4-hydroxytamoxifen and (Z)-2-[4-[1-(p-hydroxyphenyl)-2-phenyl]-1butenyl]phenoxyacetic acid

The synthesis of (Z)-4-hydroxytamoxifen and (Z)-2-[4-[1-(p-hydroxyphenyl)-2-phenyl]-1-butenyl]phenoxyacetic acid was accomplished using a McMurry reaction as the key step. The perfluorotolyl derivatives of the McMurry products enabled the separation of the minor undesirable geometrical isomer. The methodology proceeds without E,Z isomerization, employs a very mild final debenzylation step compatible with a large array of functional groups, and can be applied to the generation of a variety of 4-hydroxytamoxifen analogues.