Ligand-free Cu-catalyzed O-arylation of aliphatic diols

Zheng, Yufen; Zou, Wenxing; Luo, Laichun; Chen, Jiabei; Lin, Songwen; Sun, Qi

doi:10.1039/c5ra12529d

Cited by 14 publications

(5 citation statements)

References 45 publications

(29 reference statements)

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“…As it can be seen, copper and palladium have been utilized most frequently in the O-arylation of aliphatic alcohols. Specifically, copper catalysis was utilized toward the synthesis of ethers by Sivakumar using 2-trimethylsilylethanol, Huang using solvent quantities of alcohol alongside lithium tert -butoxide as the base, Onomura in the monoarylation of vicinal diols using diaryliodonium salts, Molander in the arylation of amino acids, Sun in the ligand-free arylation of aliphatic diols, Wu using a copper-NHC catalyst, Li in the synthesis of aromatic ethers from nonaromatic precursors, Uchiro using strongly coordinating monodentate ligands to arylate sterically hindered secondary alcohols, and Usami in the 4-alkoxylation of pyrazoles toward the synthesis of withasomnine and analogs . Palladium catalysts have been explored by Stradiotto in the comparative study of ancillary ligands for the palladium-catalyzed etherification of primary and secondary alcohols, Larrow in the O-arylation of amino alcohols, and Asachenko in the solvent-free O-arylation of primary alcohols .…”

Section: Alcohol Etherificationmentioning

confidence: 99%

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Cook,

Newman

2024

Chem. Rev.

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Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods for their functionalization require them to first be converted into a more activated derivative, while recent years have seen a vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can be used toward this goal. These transformations are broadly classified into three categories. Deoxygenative functionalizations, representing derivatization of the C−O bond, enable the alcohol to act as a leaving group toward the formation of new C−C bonds. Etherifications, characterized by derivatization of the O−H bond, represent classical reactivity that has been modernized to include mild reaction conditions, diverse reaction partners, and high selectivities. Lastly, chain functionalization reactions are described, wherein the alcohol group acts as a mediator in formal C−H functionalization reactions of the alkyl backbone. Each of these three classes of transformation will be discussed in context of intermolecular arylation, alkylation, and related reactions, illustrating how catalysis can enable alcohols to be directly harnessed for organic synthesis.

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Section: Alcohol Etherificationmentioning

confidence: 99%

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Cook,

Newman

2024

Chem. Rev.

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“…[ 45 ] Zheng and Zou experimented with coating CoAl 2 O 4 onto TiO 2 microparticles 1–5 µm in size to substantially reduce the amount of CoAl 2 O 4 pigment used. [ 26 ] CoAl 2 O 4 is a blue pigment that reflects in the NIR region and possesses a high thermal stability and refractive index. It is therefore considered as a cool pigment in heat‐reflective paints.…”

Section: Reflective Core‐shell Micro‐/nano‐structuresmentioning

confidence: 99%

“…Adapted with permission. [ 26 ] Copyright 2015, Royal Society of Chemistry. c) Photographs comparing the different shades of green of synthesized TiO 2 @CoTiO 3 core‐shell pigments with different Co:Ti ratios.…”

Section: Reflective Core‐shell Micro‐/nano‐structuresmentioning

confidence: 99%

“…[ 25 ] The core‐shell design augments the material's overall optical properties by creating an additional interface between the inner material (core) and the outer material (shell) for light reflection or refraction, while also possessing the intrinsic optical properties of both materials. An example of this is seen in a colored pigment made of a core‐shell nano‐sphere structure comprising titania (TiO 2 ) as a NIR‐reflective core and a CoAl 2 O 4 blue pigment as the shell [ 26 ] This core‐shell pigment, conventionally denoted as TiO 2 @CoAl 2 O 4 (i.e., core@shell), could achieve a high reflectance in the NIR region of light while exhibiting a bright, homogeneous blue color. Another advantage is that significantly less material is used if the material is incorporated as a shell layer in the core‐shell structure, instead of being used as a single component structure.…”

Section: Introductionmentioning

confidence: 99%

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Core‐Shell Micro‐ and Nano‐Structures for The Modification of Light‐Surface Interactions

Yeo,

Yu Tan

et al. 2023

Advanced Optical Materials

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Controlling how a material interacts with light is key to optimizing its optical properties to fit a desired function or application. The most straightforward approach is to chemically or physically modify the surface exposed to incident light. An effective method of surface modification is based on the addition of core‐shell structures at the surface. Of particular importance to many technological applications are core‐shell structures with dimensions comparable to the wavelengths of light extending from the UV up to the near‐IR region of the electromagnetic spectrum, which coincides with the major part of the solar spectrum. Surface modification approaches to tailor the optical properties of materials in this range of wavelengths are increasingly relevant in the context of materials and devices used in sustainable energy applications, such as solar cells and heat‐reflective paints. These materials are useful to mitigate the current energy and climate crises by allowing for enhanced energy harvesting and improved thermal management, respectively. Here, recent progress in the fabrication and application of core‐shell micro‐/nano‐structures for the modification of light interaction with surfaces is highlighted. Some limitations and future directions for the design of core‐shell materials are also discussed.

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“…As a result, copper-catalyzed cross-coupling reactions have become one of the most versatile carbon–heteroatom bond-forming methodologies for constructing pharmaceutical targets, agrochemicals, and polymers . For instance, Buchwald and others illustrated the utility of copper catalysis in the cross-couplings of aryl halides with alkyl alcohols (Scheme A) as a powerful method for C(sp 2 )–O bond formation . However, the incorporation of alkyl halides to generate C(sp 3 )–O bonds remains elusive.…”

Section: Introductionmentioning

confidence: 99%

Diastereoselective sp³ C–O Bond Formation via Visible Light-Induced, Copper-Catalyzed Cross-Couplings of Glycosyl Bromides with Aliphatic Alcohols

Dickson

Loka

et al. 2020

ACS Catal.

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Copper-catalyzed cross-coupling reactions have become one of the most powerful methods for generating carbon− heteroatom bonds, an important framework of many organic molecules. However, copper-catalyzed C(sp 3 )−O cross-coupling of alkyl halides with alkyl alcohols remains elusive because of the sluggish nature of oxidative addition to copper. To address this challenge, we have developed a catalytic copper system, which overcomes the copper oxidative addition barrier with the aid of visible light and effectively facilitates the cross-couplings of glycosyl bromides with aliphatic alcohols to afford C(sp 3 )−O bonds with high levels of diastereoselectivity. Importantly, this catalytic system leads to a mild and efficient method for stereoselective construction of α-1,2-cis glycosides, which are of paramount importance, but challenging. In general, stereochemical outcomes in α-1,2-cis glycosidic C−O bond-forming processes are unpredictable and dependent on the steric and electronic nature of protecting groups bound to carbohydrate coupling partners. Currently, the most reliable approaches rely on the use of a chiral auxiliary or hydrogen-bond directing group at the C2-and C4-position of carbohydrate electrophiles to control α-1,2-cis selectivity. In our approach, earthabundant copper not only acts as a photocatalyst and a bond-forming catalyst, but also enforces the stereocontrolled formation of anomeric C−O bonds. This cross-coupling protocol enables highly diastereoselective access to a wide variety of α-1,2-cis-glycosides and biologically relevant α-glycan oligosaccharides. Our work provides a foundation for developing new methods for the stereoselective construction of natural and unnatural anomeric carbon(sp 3 )−heteroatom bonds.

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Ligand-free Cu-catalyzed O-arylation of aliphatic diols

Cited by 14 publications

References 45 publications

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Core‐Shell Micro‐ and Nano‐Structures for The Modification of Light‐Surface Interactions

Diastereoselective sp³ C–O Bond Formation via Visible Light-Induced, Copper-Catalyzed Cross-Couplings of Glycosyl Bromides with Aliphatic Alcohols

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Ligand-free Cu-catalyzed O-arylation of aliphatic diols

Cited by 14 publications

References 45 publications

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Core‐Shell Micro‐ and Nano‐Structures for The Modification of Light‐Surface Interactions

Diastereoselective sp3 C–O Bond Formation via Visible Light-Induced, Copper-Catalyzed Cross-Couplings of Glycosyl Bromides with Aliphatic Alcohols

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Product

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Diastereoselective sp³ C–O Bond Formation via Visible Light-Induced, Copper-Catalyzed Cross-Couplings of Glycosyl Bromides with Aliphatic Alcohols