Facile syntheses of building blocks for the construction of phosphotyrosine mimetics

Abstract

The copper-catalysed zinc phosphonate chemistry described by Yokomatsu and Shibuya can be used to enter the classical organometallic coupling repertoire via Stille and Suzuki–Miyaura couplings. 1,4-Diiodobenzene underwent coupling with the organozinc reagent derived from diethyl bromodifluoromethylphosphonate with copper(I) catalysis to afford diethyl (4-iodophenyl)difluoromethylphosphonate. Higher yielding couplings were run with (4-trifluoromethylsulfonyloxy)- and (4-nonafluorobutylsulfonyloxy)-iodobenzenes. The iodide and the triflate coupled under palladium-catalysed conditions with a range of stannanes and boronic acids in moderate to excellent yields. Shibuya–Yokomatsu couplings were also successful with more functionalised iodoarenes and heteroarenes presenting the important phosphate mimic on a range of scaffolds

Suzuki–Miyaura Cross‐Coupling Reactions of Alkylboronic Acid Derivatives or Alkyltrifluoroborates with Aryl, Alkenyl or Alkyl Halides and Triflates

“…Cockerill and co-workers and Langer and coworkers, for example, have introduced n-alkyl chains onto aryl triflates with Pd(PPh 3 ) 4 as catalyst (Scheme 56). [79,80] With PdCl 2 (dppf) as catalyst and Cs 2 CO 3 or K 2 CO 3 as bases, a variety of aryl triflates were coupled with methylboronic acid or 2-phenylboronic acid (Scheme 57). [16] The yields of the reactions with various aryl triflates were high Scheme 56. regardless of the position of the functional group on the ring, and even the nitro group was tolerated.…”

Electrolytic partial fluorination of organic compounds 84

“…Diethyl a-fluoro-4-methoxybenzylphosphonate (1a) [14], diethyl a,a-difluoro-4-methoxybenzylphosphonate (1b) [19], diethyl a,a-difluoro-2-methoxybenzylphosphonate (2b) [19], diethyl a-fluorobenzylphosphonate (4a) [14], and diethyl a,adifluoro-4-iodobenzylphosphonate (5b) [20] were identified by spectroscopic data in the references.…”

“…1 H NMR (270 MHz), 13 C NMR (68 MHz) and 19 F NMR (254 MHz) spectra were determined using CDCl 3 as a solvent.…”

Current methods for the synthesis of 2-substituted azoles

“…147,148 The coupling of stannane 144 with either aryl triflate or iodide 152 gave comparable yields (Scheme 68) for the construction of fluorinated phosphotyrosine mimetics. 149 Silylated cytosine adduct 156 was prepared by Gronowitz and co-workers 150 …”