Metal catalyst-free photo-induced alkyl C–O bond borylation

Ma, Guobin; Chen, Changzhou; Talukdar, Sangita; Zhao, Xinluo; Lei, Chuanhu; Gong, Hegui

doi:10.1039/d0cc04776g

Cited by 22 publications

(21 citation statements)

References 43 publications

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“…A recent example can be given by the work of Geetharani and co-workers (late 2020, Scheme 6); [96] (v) decarboxylative borylation via N-hydroxyphthalimide (NHPI) esters 9 described first by Baran [97] and Aggarwal [98] groups in 2017 (Scheme 7); (vi) deoxygenative borylation of (thio)esters 10 and related compounds. While the first paper by Friese and Studer was published as late as in 2019 (Scheme 8), [99] several modifications of this method were already described; [100][101][102] (vii) deaminative borylation of primary amines via stable Katritzky salts 11 developed by Aggarwal [103] and Glorious [104] groups in 2018 (Scheme 9); (viii) borylation via CÀ H activation. Iridium-catalyzed version of this method was proposed by Hartwing and co-workers (Scheme 10); [105] enantioselective modifications were also described.…”

Section: Synthesis Of Saturated (Hetero)aliphatic Boronatesmentioning

confidence: 99%

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

2021

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Current medicinal chemistry relies heavily on the quality of building blocks, i. e. reagents used to introduce chemical diversity into the target molecules. The last decade witnessed an emergence of many novel (or well-overlooked old) chemotypes for drug discovery, which is related to adapting new synthetic methodologies, designing new sp 3 -enriched bioisosteres, paying attention to previously underrated (or even unwanted) structural motifs, or combination thereof. In this review with 532 references, a survey of selected chemotypes that emerged recently in medicinal chemistry is provided, with a focus on the synthesis of the corresponding building blocks. Thus, saturated (hetero)aliphatic boronates, sulfonyl fluorides, sulfinates, non-classical sp 3 -enriched benzene isosteres, bicyclic morpholine/piperidine/piperazine analogs, as well as gemdifluorinated cycloalkanes (as an example of emerging fluorinated motifs) are discussed.

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Section: Synthesis Of Saturated (Hetero)aliphatic Boronatesmentioning

confidence: 99%

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

2021

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“…Recently,t rapping alkyl radical intermediates by diboronc ompounds has opened an ew avenuef or the access to various aliphatic boronic esters ( Figure 1B). [16] To date, various radical precursors including alkyl halides, [17][18][19][20][21] carboxylic acid, [22][23][24][25][26] amine, [27][28][29] and alcohol derivatives [30][31][32] have been revealed as applicable substrates for radicalb orylations. Available substrates are restricted, however, by their own reduction potentials because the generation of alkyl radicali ntermediates from the substrates relies on single electron transfer (SET) in almost all cases.…”

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confidence: 99%

(o‐Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors

Suzuki

Nishimoto

Yasuda

2020

Chemistry A European J

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DedicatedtoProfessor Ilhyong Ryu on the occasion of his 70th birthday Abstract: (o-Phenylenediamino)borylstannanes were newly synthesizedt oa chieve radical boryl substitutions of av ariety of alkyl radical precursors. Dehalogenative, deaminative, decharcogenative,a nd decarboxylative borylationsp roceeded in the presenceo faradical initiator to give the corresponding organic boronc ompounds. Radical clock experiments and computational studies have provided insights into the mechanism of the homolytic substitution (S H 2) of the borylstannanes with alkyl radical intermediates. DFT calculation disclosed that the phenylenediamino structure lowered the LUMO level including the vacant p-orbital on the boron atom to enhance the reactivity to alkyl radicals in S H 2. Moreover,C (sp 3)-H borylation of THF was accomplished using the triplet state of xanthone.

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“…In 2021, Lei and Gong reported a photocatalyst-free, visiblelight-mediated methodology to achieve deoxyborylation of activated secondary and tertiary alcohols (Scheme 39). [65] While tertiary alkyl methyl oxalates afforded the desired products in good yields, no reaction took place when using secondary alkyl oxalates. To combat this issue, secondary alcohols were activated by transforming them into alkyl imidazole-1carbothioates, which furnished the desired deoxyborylated products in moderate yields.…”

Section: Via Photochemistrymentioning

confidence: 99%

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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Metal catalyst-free photo-induced alkyl C–O bond borylation

Abstract: A metal catalsyt free, blue visible light-induced C–O bond borylation of unactivated tertiary alkyl methyl oxalates has been developed to furnish tertiary alkyl boronates. The secondary alcohols activated with imidazolylthionyl,...

Cited by 22 publications

References 43 publications

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

(o‐Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors

Radical Deoxyfunctionalisation Strategies

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