An alternative C–P cross-coupling route for the synthesis of novel V-shaped aryldiphosphonic acids

• Stephen J. I. Shearan,
• Enrico Andreoli and
• Marco Taddei

Beilstein J. Org. Chem. 2022, 18, 1518–1523, doi:10.3762/bjoc.18.160

• order of addition of reactants to perform the transition-metal-catalyzed C–P cross-coupling reaction, often referred to as the Tavs reaction, employing NiCl2 as a pre-catalyst in the phosphonylation of aryl bromide substrates using triisopropyl phosphite. This new method was employed in the synthesis of

• simplification of the workup procedure. Second, there is no dilution of the reaction mixture, which lends itself to an increased reaction rate. Contrary to the conventional method, this alternative method starts with the nickel(II) precatalyst and the alkyl phosphite, triisopropyl phosphite in our case, being

• respective diphosphonic ester and limiting the accumulation of an undesired, partially converted product that would need to be separated during workup. Figure 1 shows the setup for the reaction, with the solid aryl bromide in grey and the precatalyst/triisopropyl phosphite mixture in red. It is important to

Phosphonic acid: preparation and applications

• Charlotte M. Sevrain,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219

• are methyl, ethyl, isopropyl or, occasionally, n-butyl [127]. This observation is likely explained by the synthetic methods employed to prepare phosphonates that frequently made use of the Arbuzov reaction [128] involving the commercially available trimethyl, triethyl or triisopropyl phosphite [129

Ruthenium indenylidene “1^st generation” olefin metathesis catalysts containing triisopropyl phosphite

• Stefano Guidone,
• Fady Nahra,
• Alexandra M. Z. Slawin and
• Catherine S. J. Cazin

Beilstein J. Org. Chem. 2015, 11, 1520–1527, doi:10.3762/bjoc.11.166

• Stefano Guidone Fady Nahra Alexandra M. Z. Slawin Catherine S. J. Cazin EaStCHEM School of Chemistry, University of St Andrews, St Andrews, UK, KY16 9ST, UK 10.3762/bjoc.11.166 Abstract The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords “1st generation

• [10][11][12][13][24]. In order to reduce the cost of the Ru-based pre-catalyst, our group has investigated the use of phosphites as an economical alternative to phosphines. The reaction of triisopropyl phosphite with the pyridine-containing indenylidene complex [RuCl2(Ind)(SIMes)(py)] (SIMes = N,N

• -donor ligand NHC and the π-acidic triisopropyl phosphite [25][37]. Subsequently, the benzylidene analogue G-II-P(OiPr)3 was also reported. The latter displayed a typical trans-configuration, seen in other Ru pre-catalysts, and gave a similar catalytic activity to that of the phosphine-containing parent

The Eschenmoser coupling reaction under continuous-flow conditions

• Sukhdeep Singh,
• J. Michael Köhler,
• Andreas Schober and
• G. Alexander Groß

Beilstein J. Org. Chem. 2011, 7, 1164–1172, doi:10.3762/bjoc.7.135

• ; triisopropyl phosphite; Introduction The Eschenmoser coupling [1][2] is a reaction method that yields β-enaminocarbonyl derivatives of type 4 by the elimination of sulfur (sulfide contraction) from an episulfide intermediate (Scheme 1). The reaction was described for the first time by Knott in 1955 [3] and

Palladium-catalyzed formation of oxazolidinones from biscarbamates: a mechanistic study

• Benan Kilbas and
• Metin Balci

Beilstein J. Org. Chem. 2011, 7, 246–253, doi:10.3762/bjoc.7.33

• of the palladium catalyst in THF, prepared from tris(dibenzylideneacetone)dipalladium chloroform complex and triisopropyl phosphite. The resulting oxazolidinone 9 was purified by chromatography on a silica gel column to give a crystalline product in 58% yield. The structure and configuration of 9 was

• -3,3a,5a,6,6a,6b-hexahydro-2H-cyclopropa[3,4]benzo[1,2-d][1,3]oxazole-6-carboxylate (9): Tris(dibenzylideneacetone)dipalladium chloroform complex (0.2 g, 193.6 mmol) was dissolved in freshly distilled THF (20 mL) under a nitrogen atmosphere. Triisopropyl phosphite (1.6 mL) in THF (5 mL) was then added