Superbase-Catalyzed anti-Markovnikov Alcohol Addition Reactions to Aryl Alkenes

Luo, Chaosheng; Bandar, Jeffrey S.

doi:10.1021/jacs.8b00766

Cited by 60 publications

(37 citation statements)

References 85 publications

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“…in 1987, exhibit extremely high MeCN p K

_{BH^{+}}

values, such as 26.9 for monophosphazene 1 up to 42.7 for tetraphosphazene 2 (Figure ). The Schwesinger base 2 has found many applications in, for example, the anti‐Markovnikov addition of alcohols to aryl alkenes, Ullmann couplings, as well as ether deprotonation processes …”

Section: Figurementioning

confidence: 99%

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH₂)₃]⁻, Stabilized by a Weakly Coordinating Cation

et al. 2019

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The reaction of a strongly basic phosphazene (Schwesinger base) with water afforded the corresponding metastable hydroxide trihydrate [OH(OH2)3]− salt. This is the first hydroxide solvate that is not in contact with a cation and furthermore one of rare known water‐stabilized hydroxide anions. Thermolysis in vacuum results in the decomposition of the hydroxide salt and quantitative liberation of the free phosphazene base. This approach was used to synthesize the Schwesinger base from its hydrochloride salt after anion exchange in excellent yields of over 97 %. This deprotonation method can also be used for the phosphazene‐base‐catalyzed preparation of the Ruppert–Prakash reagent Me3SiCF3 using fluoroform (HCF3) as the trifluoromethyl building block and sodium hydroxide as the formal deprotonation agent.

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“…in 1987, exhibit extremely high MeCN p K

_{BH^{+}}

Section: Figurementioning

confidence: 99%

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH₂)₃]⁻, Stabilized by a Weakly Coordinating Cation

et al. 2019

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“…The low molecular weight byproduct corresponded to the poly( M3 ) homopolymer that was produced by the ROP of M3 initiated from water contaminant in the monomer or macroinitiator. On the other hand, the high molecular weight byproduct was possibly one of the intermolecularly cross-linked products formed through the reaction between the growing oxyanion and side chain olefin [30]. Thus, the crude product was purified by preparative SEC and pure P7 was isolated in 80.4% yield ( M n,NMR = 19,600 g·mol −1 , DP 1 /DP 2 /DP 3 = 33/33/25, Đ = 1.03) (Table 3).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of μ-ABC Tricyclic Miktoarm Star Polymer via Intramolecular Click Cyclization

et al. 2018

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Cyclic polymers exhibit unique physical and chemical properties because of the restricted chain mobility and absence of chain ends. Although many types of homopolymers and diblock copolymers possessing cyclic architectures have been synthesized to date, there are relatively few reports of cyclic triblock terpolymers because of their synthetic difficulties. In this study, a novel synthetic approach for μ-ABC tricyclic miktoarm star polymers involving t-Bu-P4-catalyzed ring-opening polymerization (ROP) of glycidyl ethers and intramolecular copper-catalyzed azido-alkyne cycloaddition (CuAAC) was developed. First, the t-Bu-P4-catalyzed ROP of decyl glycidyl ether, dec-9-enyl glycidyl ether, and 2-(2-(2-methoxyethoxy) ethoxy) ethyl glycidyl ether with the aid of functional initiators and terminators was employed for the preparation of a clickable linear triblock terpolymer precursor possessing three azido and three ethynyl groups at the selected positions. Next, the intramolecular CuAAC of the linear precursor successfully produced the well-defined tricyclic triblock terpolymer with narrow dispersity in a reasonable yield. The present strategy is useful for synthesizing model polymers for studying the topological effects on the triblock terpolymer self-assembly.

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“…On the other hand, phosphazene base is recently attracting more attention because of its high basicity [5]. Phosphazene easily abstracts proton from alcohol and generates conjugate base which behaves as a reaction initiator [6]. To focus on these properties, we synthesized photobase generator OXTA-P 2 tBu to generate superbase under UV irradiation by forming a salt with OXTA and 1-tertbutyl-2,2,4,4,4-pentaxyth(dimethylamino)-2 5 ,4 5catenadi(phosphazene) (P 2 tBu).…”

Section: Introductionmentioning

confidence: 99%

Structural Analysis of Ionic Photobase Generators and Lithographic Patterning of Polysilane Films Containing the Photobase Generators

Noda

Kikuchi

Ikuma

et al. 2019

J. Photopol. Sci. Technol.

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Photobase generator is recently attracting more attention because it is freed from oxygen inhibition and metal corrosion, compared to photoacid generator and photo radical generator. 2-(9-Oxoxanthen-2-yl)propionic acid (OXTA) has an absorption in the range of i-line wavelength and it can form a salt with phosphazene base (P 2 tBu). It is photobase generator (PBG) to generate an organic superbase efficiently by UV irradiation. In this study, we synthesized a series of salts of OXTA and P 2 tBu (OXTA-P 2 tBu) at several anion-cation ratio. Then, we analyzed the PBG with each ratio by pH, UV absorption and ESR, and calculated OXTA-P 2 tBu complex by (TD)B3LYP/6-31+G(d,p) level. The crystal of OXTA-P 2 tBu synthesized at optimum ratio was analyzed by single crystal X-ray diffraction and we described the crystal structure. Furthermore, we obtained nega-type pattern with polysilane solution containing OXTA-P 2 tBu in the optimum ratio.

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Superbase-Catalyzed anti-Markovnikov Alcohol Addition Reactions to Aryl Alkenes

Cited by 60 publications

References 85 publications

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH₂)₃]⁻, Stabilized by a Weakly Coordinating Cation

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH₂)₃]⁻, Stabilized by a Weakly Coordinating Cation

Synthesis of μ-ABC Tricyclic Miktoarm Star Polymer via Intramolecular Click Cyclization

Structural Analysis of Ionic Photobase Generators and Lithographic Patterning of Polysilane Films Containing the Photobase Generators

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Superbase-Catalyzed anti-Markovnikov Alcohol Addition Reactions to Aryl Alkenes

Cited by 60 publications

References 85 publications

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH2)3]−, Stabilized by a Weakly Coordinating Cation

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH2)3]−, Stabilized by a Weakly Coordinating Cation

Synthesis of μ-ABC Tricyclic Miktoarm Star Polymer via Intramolecular Click Cyclization

Structural Analysis of Ionic Photobase Generators and Lithographic Patterning of Polysilane Films Containing the Photobase Generators

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Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH₂)₃]⁻, Stabilized by a Weakly Coordinating Cation

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH₂)₃]⁻, Stabilized by a Weakly Coordinating Cation