Ti-Catalyzed Reductive Dehydroxylative Vinylation of Tertiary Alcohols

Xie, Hao; Wang, Sheng; Wang, Yuquan; Guo, Peng; Shu, Xing‐Zhong

doi:10.1021/acscatal.1c05530

Cited by 30 publications

(20 citation statements)

References 73 publications

(49 reference statements)

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“…1) Use of unactivated alcohols as radical precursors Some advancements have been made in this area, particularly with the use of Ti-based catalysts. [25][26] However, most deoxyfunctionalisation reactions require the use of large activating groups, which decrease the overall atom economy of the process. In addition, the resulting by-products can present challenges during product purifications (e.g., phospine oxides).…”

Section: Discussionmentioning

confidence: 99%

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Radical Deoxyfunctionalisation Strategies

Anwar

Merkens

Troyano

et al. 2022

Preprint

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Due to their abundance and readily available synthesis, alcohols provide ideal handles for the selective derivatisation of organic molecules. Radical chemistry offers versatile strategies for the conversion of Csp3–O bonds into a wide range of Csp3–C or Csp3–heteroatom bonds. In these reactions, alcohols are readily derivatised with an activator group which can undergo facile mesolysis to generate a primary, secondary, or tertiary open-shell species that can engage in further transformations. These strategies are particularly effective at overcoming steric limitations associated with nucleophilic substitution pathways. Despite their potential, the use of radical deoxyfunctionalisation reactions as a general strategy for the synthesis of useful and complex molecules remains underutilised. Herein, we highlight recent advancements in this exciting field using photocatalysis, transition metal catalysis or electrochemistry to initiate the radical processes.

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Section: Discussionmentioning

confidence: 99%

“…The authors have also recently expanded this strategy for the selective dehydroxylative vinylation of tertiary alcohols. [26] Scheme 14. Ti-catalysed alkylation using free aliphatic alcohols.…”

Section: Via Transition Metal Catalysismentioning

confidence: 99%

Radical Deoxyfunctionalisation Strategies

Anwar

Merkens

Troyano

et al. 2022

Preprint

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“…Finally, the same authors recently reported a Ti‐mediated dehydroxylative vinylation method to form quaternary centres (Scheme 31). [51] This protocol showed a high regioselectivity for tertiary alcohols, coupled with a wide range of vinyl halides (F, Cl, Br and I). Mechanistically, the methodology follows the same pathway proposed previously in their alkylation methodology (see Scheme 17).…”

Section: Deoxygenative C−c Bond Formationmentioning

confidence: 97%

“…Some advancements have been made in this area, particularly with the use of Ti-based catalysts. [28,51] However, most deoxyfunctionalisation reactions require the use of large activating groups, which decrease the overall atom economy of the process. In addition, the resulting by-products can present challenges during product purifications (e. g., phosphine oxides).…”

Section: Use Of Unactivated Alcohols As Radical Precursorsmentioning

confidence: 99%

Radical Deoxyfunctionalisation Strategies**

et al. 2022

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Due to their abundance and readily available synthesis, alcohols provide ideal handles for the selective derivatisation of organic molecules. Radical chemistry offers versatile strategies for the conversion of Csp3−O bonds into a wide range of Csp3−C, Csp3−H, or Csp3−heteroatom bonds. In these reactions, alcohols are readily derivatised with an activator group which can undergo facile mesolysis to generate a primary, secondary, or tertiary open‐shell species that can engage in further transformations. These strategies are particularly effective at overcoming steric limitations associated with nucleophilic substitution pathways. Despite their potential, the use of radical deoxyfunctionalisation reactions as a general strategy for the synthesis of useful and complex molecules remains underutilised. In this Review, we highlight recent advancements in this exciting field in which photocatalysis, transition metal catalysis or electrochemistry are used to initiate the radical processes.

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“…17 Shu has also demonstrated that Cp*TiCl3 can be applied to a dehydroxylative radical vinylation reaction of tertiary alcohols with vinyl halides in the presence of a reductant and TESCl (Scheme 7). 18 The reaction proceeded with a broad scope of alcohols and vinyl halides, affording various products with allcarbon quaternary centers. It is worth noting that the method is highly selective for tertiary alcohols, leaving 1°/2° alkyl-OH (Bn-OH included) and Ar-OH intact.…”

Section: Scheme 4 Ti-mediated Alcohol C-o Radical Homolysismentioning

confidence: 99%

Recent Progress on Transition-Metal-Mediated Reductive C(sp3)–O Bond Radical Addition and Coupling Reactions

Lin

Chen

et al. 2022

Synthesis

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In this mini review, we summarized the recent development of thermo-driven C(sp3)‒O bond radical scission methods and their applications in the construction of C(sp3)‒C bonds via conjugate additions with activated double bonds and reductive coupling mediated by economic 3d metals, in particular nickel. We assort the review based on the approaches of C(sp3)‒O bond radical scission in three folds (see below). Upon creation of the radical intermediates, subsequent transformation into C(sp3)‒C bonds that enables C(sp3)‒O cross-electrophile coupling with carbon electrophiles are discussed in depth. 1. Direct SET to C(sp3)‒O bond 2. Radical scission of activated C(sp3)‒O bonds via SET to the protecting groups 3. In situ activation of alcohols 4. Summary and outlook

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Ti-Catalyzed Reductive Dehydroxylative Vinylation of Tertiary Alcohols

Cited by 30 publications

References 73 publications

Radical Deoxyfunctionalisation Strategies

Radical Deoxyfunctionalisation Strategies

Radical Deoxyfunctionalisation Strategies**

Recent Progress on Transition-Metal-Mediated Reductive C(sp3)–O Bond Radical Addition and Coupling Reactions

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