Regio- and Stereo-Selective Intermolecular Hydroamidation of Ynamides: An Approach to (<i>Z</i>)-Ethene-1,2-Diamides

Peng, Zhiyuan; Zhang, Zhenming; Tu, Yongliang; Zeng, Xianzhu; Zhao, Junfeng

doi:10.1021/acs.orglett.8b02409

Cited by 23 publications

(9 citation statements)

References 38 publications

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“…Dodd and co‐workers reported that trans ‐selective β ‐addition of indoles to ynamides is an efficient strategy to furnish functionalized indoles . Very recently, our group discovered that the base‐promoted hydroamidation of ynamides is a general synthetic strategy for ( Z )‐ethene‐1,2‐diamides with excellent regio‐ and stereoselectivity . Thus inspired, we envisioned that the synthesis of ( Z )‐ β ‐phosphor‐enamides would be possible if the base‐promoted hydrophosphorylation of ynamides could be realized.…”

Section: Figuresupporting

confidence: 79%

“…[18] Considering the potential applications of (Z)-β-phosphor-enamides, efficient strategies for their synthesis are in great demand. [21] Thus inspired, we envisioned that the synthesis of (Z)-β-phosphor-enamides would be possible if the base-promoted hydrophosphorylation of ynamides could be realized. [19] Dodd and co-workers reported that trans-selective β-addition of indoles to ynamides is an efficient strategy to furnish functionalized indoles.…”

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confidence: 99%

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Regio‐ and Stereoselective Hydrophosphorylation of Ynamides: A Facile Approach to (Z)‐β‐Phosphor‐Enamides

et al. 2019

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The first trans-selective β-hydrophosphorylation of ynamides, which provides a facile approach to (Z)-β-phosphor-enamide derivatives in moderate to excellent yields and with excellent regio-and stereoselectivity, is described. This transition-metal-free reaction is featured with operationally simple procedure, mild reaction conditions, readily available starting materials, broad substrate scope and good functional-group tolerance. It is noted that the (Z)-β-phosphor (V)-enamides can be prepared from the oxidation of the corresponding phosphine derivatives or the direct β-hydrophosphorylation of ynamides with diphenylphosphine oxide. In addition, cis-trans isomerization of (Z)-βphosphor (V)-enamides can be easily realized to furnish the corresponding (E)-β-phosphor (V)-enamides. This advantageous feature enables the preparation of (Z)-β-phosphor (V)-enamides as well as (E)-β-phosphor (V)-enamides from the same starting materials.Scheme 2. Hydrophosphorylation of Ynamides with Diphenylphosphine. Reaction conditions: 1 (0.2 mmol), 4 a (0.24 mmol) and Cs 2 CO 3 (0.1 mmol) in DMSO (1.0 mL) at rt for 10 min under N 2 to afford products 5, and then H 2 O 2 (1.1 equiv.) or S 8 (0.5 equiv.) was added for 5 min afford products 3 or 6. Z:E > 99:1 (determined by crude 1 H NMR).Scheme 3. Reduction and Z/E-isomerization of (Z)-hydrophosphor (V)-enamides.

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confidence: 79%

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Regio‐ and Stereoselective Hydrophosphorylation of Ynamides: A Facile Approach to (Z)‐β‐Phosphor‐Enamides

et al. 2019

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“…Finally, Yin and co-workers reported an interesting novel dual photoredox/Ni catalysed reductive migratory cross-coupling of alkyl bromides with aryl bromides 649. [132] Using diisopropylamine as the terminal reductant, primary and secondary alkyl bromides were successfully added to the transitory Ni complex and migrated toward the benzylic position to form benzylic arylation products with a very good selectivity for the migration product. Examples of such migration were reported previously in the literature with many different transition metals, including Nickel (Scheme 98).…”

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Synergistic Photoredox/Transition‐Metal Catalysis for Carbon–Carbon Bond Formation Reactions

2019

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Carbon–carbon bond formation reactions are of longstanding interest in organic chemistry. Improvements of the methods targeting its creation are still being performed, especially thanks to the development of innovative methodologies in transition metal catalysis and photocatalysis. This review will tackle the combination of transition metal and photoredox cycles to create carbon–carbon bonds, focusing on the four transition metals most reported in the literature in this domain: Ni, Pd, Au and Cu.

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“…[68][69][70][71] We have recently disclosed that ynamides could be used as novel coupling reagents for facilitating amide 72-73 and ester 74-75 bond formation, which were accomplished by taking advantage of the α-addition of carboxylic acid to ynamides (Figure 2a). 71 Furthermore, we have found that the regioselectivity could be reversed by employing basic reaction conditions as exemplified by the regio-and stereoselective hydroamidation 76 and hydrophosphorylation 77 of ynamides. These reactions proceeded smoothly via a base-promoted trans-selective β-addition with excellent regio-and stereoselectivity, which was rarely exploited compared with the extensively studied α-addition of ynamides (Figure 2b) [78][79][80] .…”

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confidence: 99%

Highly Chemo-, Regio- and Stereoselective Cysteine Modification of Peptides and Proteins with Ynamides

Wang

Zhao

Ghadir

et al. 2021

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Chemoselective modification of peptides and proteins has wide applications in chemical biology and pharmaceutical development. An efficient cysteine (Cys) precise modification protocol via rationally designed β-addition of ynamides is reported. The strong electron-withdrawing triflyl group on the nitrogen atom of ynamides plays a crucial role for controlling the chemo-, stereo- and regioselectivities of this protocol. Another substituent of the terminal ynamides offers a handle for functionality diversification. This Cys modification with ynamides proceeds efficiently in a slightly basic aqueous media (pH 8) to provide a series of Z-isomer of the corresponding conjugated products with excellent stereoselectivity (> 99%) and superior stability. All the reactive peptide side chain functional groups such as amino, carboxyl, primary amide, and hydroxyl groups, as well as the unprotected imidazole and indole rings are compatible. This method displays a broad substrates scope including linear and cyclic peptides and proteins. The potential application of this method in peptide and protein chemical biology was exemplified by Cys-bioconjugation with ynamides containing different functional molecules, including drug, fluorescent and affinity tags. In addition, this strategy is also compatible with click chemistry (performed in one pot), which remarkably extends the toolbox for further applications. The chemoselective biotinylation of ubiquitin(G47C) variant with a biotinylated ynamide, as well as the regioselective modification of Cys14 and Cys38 in bovine pancreatic trypsin inhibitor (BPTI) were accomplished under the optimized conditions and in high yield, without perturbation of disulfide bonds.

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Regio- and Stereo-Selective Intermolecular Hydroamidation of Ynamides: An Approach to (Z)-Ethene-1,2-Diamides

Cited by 23 publications

References 38 publications

Regio‐ and Stereoselective Hydrophosphorylation of Ynamides: A Facile Approach to (Z)‐β‐Phosphor‐Enamides

Regio‐ and Stereoselective Hydrophosphorylation of Ynamides: A Facile Approach to (Z)‐β‐Phosphor‐Enamides

Synergistic Photoredox/Transition‐Metal Catalysis for Carbon–Carbon Bond Formation Reactions

Highly Chemo-, Regio- and Stereoselective Cysteine Modification of Peptides and Proteins with Ynamides

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