Transformation of alkynyl sulfones into alkynylphosphonates with trialkyl phosphites

Yatsumonji, Yasutaka; Ogata, Akitoshi; Tsubouchi, Akira; Takeda, Takeshi

doi:10.1016/j.tetlet.2008.02.013

Cited by 30 publications

(13 citation statements)

References 21 publications

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“…45 Traditionally, they were prepared through nucleophilic substitution of phosphoryl halides with Li or Mg acetylides. 46 They have also been synthesized from 1,1-dibromoalkenes, 46a,47 alkynyl sulfones, 48 and copper acetylides. 49 In 2009, our group reported a copper-catalyzed dehydrogenative phosphorylation of terminal alkynes with H-phosphonates, providing a clean method for the synthesis of alkynyl phosphoryl compounds.…”

Section: Formation Of P(o)-spc Bondsmentioning

confidence: 99%

Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

et al. 2020

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Herein, we highlight advances in the phosphorylation of readily available carboxylic acids and their derivatives forming synthetically important P(O)–sp3C, P(O)–sp2C, and P(O)–spC bonds, with an emphasis on the results demonstrated since 2010. This review examines the challenges associated with the use of this strategy for the synthesis of organophosphorus compounds and details advances in the design of catalytic systems that suppress these problems thus resulting in notable progress. Mechanistic details are discussed where available.1 Introduction2 Formation of P(O)–sp3C Bonds3 Formation of P(O)–sp2C Bonds4 Formation of P(O)–spC Bonds5 Outlook and Conclusion

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Section: Formation Of P(o)-spc Bondsmentioning

confidence: 99%

Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

et al. 2020

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“…Dialkyl 1‐alkynylphosphonates can be employed synthetically as acetonyl equivalents and have also been used as Michael acceptors in cycloaddition reactions. Takeda et al have described a new approach to the synthesis of these valuable intermediates, by treatment of 1‐alkynyl sulfones with trialkyl phosphites (Scheme ) 65. This method has some advantages over other approaches that require excesses of unstable or explosive reagents 66…”

Section: Sulfonyl Acetylenes As Alkynylating Reagentsmentioning

confidence: 99%

Strongly Luminous Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, meso‐ or rac‐Bis[(diphenylphosphinomethyl)phenylphosphino]methane

Tanase

Otaki

Nishida

et al. 2014

Chemistry A European J

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A series of tetragold(I) complexes supported by tetraphosphine ligands, meso- and rac-bis[(diphenylphosphinomethyl)phenylphosphino]methane (meso- and rac-dpmppm) were synthesized and characterized to show that the tetranuclear Au(I) alignment varies depending on syn- and anti-arrangements of the two dpmppm ligands with respect to the metal chain. The structures of syn-[Au4 (meso-dpmppm)2X]X'3 (X = Cl; X' = Cl (4 a), PF6 (4 b), BF4 (4 c)) and syn-[Au4 (meso-dpmppm)2]X4 (X = PF6 (4 d), BF4 (4 e), TfO (4 f); TfO = triflate) involved a bent tetragold(I) core with a counter anion X incorporated into the bent pocket. Complexes anti-[Au4 (meso-dpmppm)2]X4 (X = PF6 (5 d), BF4 (5 e), TfO (5 f)) contain a linearly ordered Au4 string and complexes syn-[Au4 (rac-dpmppm)2X2]X'2 (X = Cl, X' = Cl (6 a), PF6 (6 b), BF4 (6 c)) and syn-[Au4 (rac-dpmppm)2]X4 (X = PF6 (6 d), BF4 (6 e), TfO (6 f)) consist of a zigzag tetragold(I) chain supported by the two syn-arranged rac-dpmppm ligands. Complexes 4 d-f, 5 d-f, and 6 d-f with non-coordinative large anions are strongly luminescent in the solid state (λmax = 475-515 nm, Φ = 0.67-0.85) and in acetonitrile (λmax = 491-520 nm, Φ = 0.33-0.97); the emission was assigned to phosphorescence from (3) [dσ*σ*σ* pσσσ] excited state of the Au4 centers on the basis of DFT calculations as well as the long lifetime (a few μs). The emission energy is predominantly determined by the HOMO and LUMO characters of the Au4 centers, which depend on the bent (4), linear (5), and zigzag (6) alignments. The strong emissions in acetonitrile were quenched by chloride anions through simultaneous dynamic and static quenching processes, in which static binding of chloride ions to the Au4 excited species should be the most effective. The present study demonstrates that the structures of linear tetranuclear gold(I) chains can be modified by utilizing the stereoisomeric tetraphosphines, meso- and rac-dpmppm, which may lead to fine tuning of the strongly luminescent properties intrinsic to the Au(I) 4 cluster centers.

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“…Consequently, alternative methods have been developed in recent years, most of them based on the use of transition-metal catalysts. Many of the reported methodologies require the use of functionalized starting alkenes or alkynes, including 1,1-dibromoalkenes, 5 propiolic acids, 6 metal acetylides, 7 alkynyl sulfones, 8 trialkylsilyl alkynes, 9 and 4-aryl-2methyl-3-butyn-2-ols. 10 For technical and economic reasons, the direct synthesis of alkynylphosphonates from commercial or readily available starting alkynes is the most attractive way for the synthesis of these phosphorus compounds.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Consequently, alternative methods have been developed in recent years, most of them based on the use of transition-metal catalysts. Many of the reported methodologies require the use of functionalized starting alkenes or alkynes, including 1,1-dibromoalkenes, propiolic acids, metal acetylides, alkynyl sulfones, trialkylsilyl alkynes, and 4-aryl-2-methyl-3-butyn-2-ols . For technical and economic reasons, the direct synthesis of alkynylphosphonates from commercial or readily available starting alkynes is the most attractive way for the synthesis of these phosphorus compounds.…”

Section: Introductionmentioning

confidence: 99%

“…Different copper sources were then tested as catalysts. As shown in Table 1 (entries [7][8][9][10] CuCl, CuCl 2 and CuI failed in catalyzing the cross-coupling reaction, whereas CuO gave only 38% of conversion into the alkynylphosphonate product. We then optimized the catalyst loading and found that by doubling the amount of Cu 2 O (10 mg, 14 mol%) the reaction yield was increased from 77% to 86% (Table 1, entry 1).…”

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confidence: 99%

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Base-Free Direct Synthesis of Alkynylphosphonates from Alkynes and H-Phosphonates Catalyzed by Cu₂O

et al. 2016

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Transformation of alkynyl sulfones into alkynylphosphonates with trialkyl phosphites

Cited by 30 publications

References 21 publications

Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

Strongly Luminous Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, meso‐ or rac‐Bis[(diphenylphosphinomethyl)phenylphosphino]methane

Base-Free Direct Synthesis of Alkynylphosphonates from Alkynes and H-Phosphonates Catalyzed by Cu₂O

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Transformation of alkynyl sulfones into alkynylphosphonates with trialkyl phosphites

Cited by 30 publications

References 21 publications

Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

Strongly Luminous Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, meso‐ or rac‐Bis[(diphenylphosphinomethyl)phenylphosphino]methane

Base-Free Direct Synthesis of Alkynylphosphonates from Alkynes and H-Phosphonates Catalyzed by Cu2O

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Base-Free Direct Synthesis of Alkynylphosphonates from Alkynes and H-Phosphonates Catalyzed by Cu₂O