A novel mode of access to polyfunctional organotin compounds and their reactivity in Stille cross-coupling reaction

Lamandé‐Langle, Sandrine; Abarbri, Mohamed; Thibonnet, J.; Duchêne, Alain

doi:10.1016/j.jorganchem.2009.03.030

Cited by 11 publications

(9 citation statements)

References 55 publications

(11 reference statements)

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“…Before use, the purity of 3 was verified by NMR spectroscopy (Table 1). Only limited NMR spectroscopic data have been reported for 3b so far [10] and the NMR spectra for 3d in Figure 1 show the purity that can be achieved. In the case of 3a, the molecular structure was established by X-ray crystallography ( Figure 2).…”

Section: Bis(trimethylsilylethynyl)tin Compoundsmentioning

confidence: 99%

Selective Synthesis of Stannoles by 1,1‐Carboboration of Bis(trimethylsilylethynyl)tin Compounds Using Weakly and Strongly Electrophilic Triorganoboranes: Characterization of a Zwitterionic Intermediate

et al. 2014

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The triorganoboranes BEt 3 , BPh 3 , and B(C 6 F 5 ) 3 were allowed to react with bis(trimethylsilylethynyl)diorganotin com-n Oct (c), Ph (d)] to give selectively and quantitatively stannoles. The reactions proceeded by 1,1-carboboration in two consecutive steps (inter-and intramolecular) and intermediates were detected by NMR spectroscopy. In one case, using the strongly electrophilic B(C 6 F 5 ) 3 , a zwitterionic inter-

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Section: Bis(trimethylsilylethynyl)tin Compoundsmentioning

confidence: 99%

Selective Synthesis of Stannoles by 1,1‐Carboboration of Bis(trimethylsilylethynyl)tin Compounds Using Weakly and Strongly Electrophilic Triorganoboranes: Characterization of a Zwitterionic Intermediate

et al. 2014

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“…Despite their toxicity, organostannates are versatile reagents to accomplish a variety of metalmediated couplings, the Stille reaction in particular. In 2009 Lamandé-Langle et al described a general procedure that allows the efficient synthesis of various organotin compounds in following a Barbier-like strategy as well (Scheme 8) [35]. The process offers a number of advantages such as simplicity and good yields, and reagent quality (both solvents and tin halides) does not constitute a critical issue.…”

Section: Main Group Metal Derivativesmentioning

confidence: 99%

Merging Metallic Catalysts and Sonication: A Periodic Table Overview

et al. 2017

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Abstract:This account summarizes and discusses recent examples in which the combination of ultrasonic waves and metal-based reagents, including metal nanoparticles, has proven to be a useful choice in synthetic planning. Not only does sonication often enhance the activity of the metal catalyst/reagent, but it also greatly enhances the synthetic transformation that can be conducted under milder conditions relative to conventional protocols. For the sake of clarity, we have adopted a structure according to the periodic-table elements or families, distinguishing between bulk metal reagents and nanoparticles, as well as the supported variations, thus illustrating the characteristics of the method under consideration in target synthesis. The coverage focuses essentially on the last decade, although the discussion also strikes a comparative balance between the more recent advancements and past literature.

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“…The organotins used in Stille cross-coupling were prepared by sonochemistry. 20 Stille and Suzuki palladium cross-coupling was performed on the arylic bromide of previously prepared (E)-allylarene intermediates I 1a-h,j to obtain the desired styrenes 3a-m. This Stille reaction was run in classical coupling arylic halide conditions with vinyltin in toluene at 90 °C for 18 hours, with a small excess of vinyltin for optimal reaction progress.…”

Section: Synthesis Of Substituted Styrenes (Types I and Ii): Cross-comentioning

confidence: 99%

“…1, 127.0 (2 C), 127.7, 128.2, 128.8, 128.9, 129.1 (2 C), 129.4, 129.5, 130.0 (2 C), 130.5 (2 C), 135.2, 137.6, 138.2, 140.6, 148.7, 192 13 C NMR (50.3 MHz, CDCl 3 ): δ = -1.12 (3 C), 36.3, 124.5, 125.7, 127 (2 C), 127.3, 129.4 (2 C), 131.2, 137.1, 140.5, 142.4, 144.6 136.0,137.3,138.6,141.4,146.5. MS (EI,70 eV): m/z = 441 (M +• -57 , 90), 385 (31), 325 (26), 191 (26), 179 20, 177 20, 165 (12), 163 14, 121 25, 105 (100), 91 (20), 57 18, 41 (46), 39 (15). 13 C NMR (50.3 MHz, CDCl 3 ): δ = 30.1 (3 C), 33.9, 42.5, 124.6, 124.9, 127.3, 127.9, 129.3, 130.0 (2 C), 130.5 (2 C), 135.…”

Section: Compounds 4a-g By Stille Reaction; General Proceduresmentioning

confidence: 99%

Efficient Synthesis of Substituted Styrenes and Biaryls (or Heteroaryls) with Regioselective Reactions of ortho-, meta-, and para-Bromobenzyl Bromide

Anselmi¹,

Abarbri

Duchêne

et al. 2012

Synthesis

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Regio-and stereoselective reactions of ortho-, meta-, and para-bromobenzyl bromide under Stille and (or) Suzuki crosscoupling reactions are described that provided substituted styrene monomers and biaryls in two steps. By controlling the experimental conditions, the first coupling provided access to allylarene or diarylmethane intermediates, and the second reaction led to the desired styrenes and biaryls, substituted by a spacer arm in the ortho, meta or para position depending on the starting material.Styrenes and biaryls are useful building blocks for fine chemical synthesis. 1,2 Biaryl moieties with important physical or biological properties are widely represented in organic molecules. 3 As pharmacophores, they are found in many medicinally important compounds such as antibiotic, anti-inflammatory, antihypertensive, and anticancer drugs, among others. Di-or triaromatic rings are the backbone of some of the most efficient and selective ligands for asymmetric catalysis, especially when atropoisomerism is possible. 4Styrenes are of particular interest as monomers in the polymer industry, 5 conferring different properties on the polymers depending on the nature of the substituents present on the derivatives. The development of efficient, selective, and high-yielding methods for the preparation of these molecules will, therefore, continue well into the future. In continuation of our previous studies on the different reactions of the two bromine atoms of bromobenzyl bromide 6 by cross-coupling reactions and recognizing that a chemoselective reaction could be valuable, we have developed an efficient and versatile method to synthesize a wide range of styrenes and biaryls very easily and selectively. We have investigated the selective substitution reaction under two successive Stille 7 and Suzuki 7g,8 crosscoupling reactions with o-, m-, and p-bromobenzyl bromides (Scheme 1). Scheme 1 Preparation of styrene and biaryl compoundsThe first coupling permitted regioselective access to allylarene or diarylmethane intermediates I and II, and the second reaction allowed the synthesis of styrenes and biaryls. Synthesis of Intermediates I and IIUsing 0.95 to 1 equivalents of an organometallic reagent and starting from o-, m-or p-bromobenzyl bromides, we were able to substitute benzylic bromide, rather than arylic bromide, regioselectively by Stille or Suzuki cross-coupling reactions in the presence of a palladium salt. The regioselective reaction of these two types of bromide has already been demonstrated by other reactions (e.g., nucleophilic or metallic substitution), however few reports have investigated this regioselectivity by cross-coupling catalysis. 6,9 We accessed bromo-substituted allylarenes 1a-j (intermediates I) or brominated diarylmethanes 1k-r (intermediates II) depending on the type of palladium catalysis and the organometallic reagent used. The reaction conditions were classical (Table 1), but the temperature of the reaction should not exceed 80 °C, otherwise partial isomerization of the double bond of the ally...

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A novel mode of access to polyfunctional organotin compounds and their reactivity in Stille cross-coupling reaction

Cited by 11 publications

References 55 publications

Selective Synthesis of Stannoles by 1,1‐Carboboration of Bis(trimethylsilylethynyl)tin Compounds Using Weakly and Strongly Electrophilic Triorganoboranes: Characterization of a Zwitterionic Intermediate

Selective Synthesis of Stannoles by 1,1‐Carboboration of Bis(trimethylsilylethynyl)tin Compounds Using Weakly and Strongly Electrophilic Triorganoboranes: Characterization of a Zwitterionic Intermediate

Merging Metallic Catalysts and Sonication: A Periodic Table Overview

Efficient Synthesis of Substituted Styrenes and Biaryls (or Heteroaryls) with Regioselective Reactions of ortho-, meta-, and para-Bromobenzyl Bromide

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