Palladium-Catalyzed Alkynylation of Morita–Baylis–Hillman Carbonates with (Triisopropylsilyl)acetylene on Water

Li, Yangxiong; Liu, Li; Kong, De‐Long; Wang, Dong; Feng, Weichun; Yue, Tao; Li, Chao‐Jun

doi:10.1021/acs.joc.5b00728

Cited by 19 publications

(5 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Liu and co-workers examined the palladiumcatalysed alkynylation of Morita-Balyis-Hillman carbonates with substituted acetylenes using on-water conditions. 63 A range of ligands were examined for the reaction and the [Pd:NHC] 107 was found to give the optimum yield (Scheme 22c). When the reaction of triisopropylsilaneacetylene 104 was reacted with compound 105 in THF the product was isolated in a yield of 20%.…”

Section: Organometallic and Transition Metal Catalysed Reactionsmentioning

confidence: 99%

See 1 more Smart Citation

Organic synthesis reactions on-water at the organic–liquid water interface

2016

View full text Add to dashboard Cite

Organic reactions that occur at the water interface for water-insoluble compounds, and reactions in water solution for water soluble compounds, has added a powerful dimension to prospects for organic synthesis under more beneficial economic and environmental conditions. Many organic molecules are partially soluble in water and reactions that appear as heterogeneous mixtures and suspensions may involve on-water and in-water reaction modes occurring simultaneously. The behavior of water molecules and organic molecules at this interface is discussed in the light of reported theoretical and experimental studies. The on-water catalytic effect, relative to neat reactions or organic solvents, ranges from factors of several hundred times to 1-2 times and it depends on the properties of reactant compounds. In some cases when on-water reactions produce quantitative yields of water-insoluble products they can reach ideal synthetic aspirations.

show abstract

Section: Organometallic and Transition Metal Catalysed Reactionsmentioning

confidence: 99%

“…The use of water as a solvent has prompted debate as to whether reactions occur on-water, in-water or in Scheme 22 Transition metal catalysed reactions using on-water conditions. 60,62,63 the presence of water. However the true nature of these reactions need further in-depth mechanistic study to determine the exact role water plays.…”

Section: Organocatalysismentioning

confidence: 99%

Organic synthesis reactions on-water at the organic–liquid water interface

2016

View full text Add to dashboard Cite

show abstract

“…Therefore, much attention has been paid to the synthesis of allylic amines. A number of allylic surrogates, such as alkynes, [4] olefins, [5] allylic amines, [6] allylic esters, [7] allylic ethers, [8] and allylic alcohols [9] were developed and used in Tsuji-Trost reactions. Among them, the direct use of allylic alcohols is much attractive, because of that allylic alcohol is much cheap and easily-available, and moreover the Tsuji-Trost reaction of allylic alcohols liberates water as the sole byproduct, showing the idea of green chemistry.…”

Section: Introductionmentioning

confidence: 99%

Pd‐Catalyzed Dehydrative Synthesis of Allylic Amines in Water

Yan

Liu

et al. 2023

Asian J Org Chem

View full text Add to dashboard Cite

A mild Pd‐catalyzed Tsuji‐Trost reaction of allylic alcohols with an amine nucleophile in water media was developed, leading to the green synthesis of the valuable allylic amines. This new method requires no chemical activators and sophisticated soluble ligands, and can be easily scaled up in gram scale and be readily extended to the gram scale synthesis of Naftifine, one of the best‐selling antifungal drugs, showing the practical value of this new method.

show abstract

“…Alternative methods have also been developed for alkyne coupling, which avoid the need for a halide precursor or for a Cu cocatalyst. Thus, under Pd-catalyzed conditions, terminal alkynes have undergone conjugate addition to α,β-unsaturated carbonyl derivatives, − cross-addition to ynol ethers, and oxidative C sp2 –C sp coupling. − In a broader synthetic context, the general field of metal-catalyzed heterocyclization–coupling reactions (Scheme b) has been the subject of continuing attention because it provides access to functionalized heterocyclic structures with useful applications. The particular case of palladium-catalyzed heterocyclization–alkynylation cascades (Scheme c) is also known, − but it has received comparatively little attention despite its potential for the incorporation of alkynyl groups onto heterocyclic frameworks.…”

Section: Introductionmentioning

confidence: 99%

Regioselective Palladium-Catalyzed Heterocyclization–Sonogashira Coupling Cascades from 2-Alkynylbenzamides and Terminal Alkynes: Experimental and DFT Studies

et al. 2018

View full text Add to dashboard Cite

A regioselective heterocyclization–Sonogashira coupling cascade between 2-alkynylbenzamides and terminal alkynes is described. The reaction proceeds under Pd(II) catalysis, with air used as a terminal oxidant to regenerate the catalyst from the Pd(0) produced in the C–C coupling. The cascade process provides alkynyl-substituted isobenzofuranimine products in a single operation. These products are the result of a 5-exo O-cyclization, while products derived from the alternative 6-endo cyclization mode are observed in minor amounts. Two competing mechanisms have been considered to account for the observed results. Both involve heterocyclization, alkyne C–H activation, and reductive elimination steps but differ in the relative order of the first two. Control experiments using a preformed alkynylpalladium complex have shown that a mechanism starting with alkyne C–H activation is viable. On the other hand, DFT calculations indicate that the alternative cyclization-first mechanism is also competitive, particularly when PPh3 is used as ligand. Calculations also suggest that the exo cyclization is favored over the endo mode by the presence of PPh3 and σ-C Pd ligands in the activated complex undergoing cyclization.

show abstract

Palladium-Catalyzed Alkynylation of Morita–Baylis–Hillman Carbonates with (Triisopropylsilyl)acetylene on Water

Cited by 19 publications

References 45 publications

Organic synthesis reactions on-water at the organic–liquid water interface

Organic synthesis reactions on-water at the organic–liquid water interface

Pd‐Catalyzed Dehydrative Synthesis of Allylic Amines in Water

Regioselective Palladium-Catalyzed Heterocyclization–Sonogashira Coupling Cascades from 2-Alkynylbenzamides and Terminal Alkynes: Experimental and DFT Studies

Contact Info

Product

Resources

About