eEtherification: An Electrochemical Strategy toward the Synthesis of Sterically Hindered Dialkyl Ethers from Activated Alcohols DOI
Cyrille Kiaku, Simon Kaltenberger, Daniel Raydan

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 17, 2024

Traditional etherification methods, although staples in synthetic chemistry, often fall short the efficient construction of sterically hindered dialkyl ethers, especially under mild and practical conditions. Recent advances have attempted to address these limitations, typically relying on transition metal catalysts, external reductants, or harsh reaction In this work, we disclose a novel electrochemical approach that enables synthesis ethers from economically relevant readily accessible alcohols without need for sacrificial oxidants. Our protocol exploits conditions generate reactive carbocations, which are subsequently captured by alcohol nucleophiles yield desired ethers. This method is cost-effective, practical, broad scope, providing valuable addition chemists' toolkit ether synthesis.

Язык: Английский

Stereoselective amino acid synthesis by synergistic photoredox-pyridoxal radical biocatalysis DOI
Lei Cheng, Dian Li, Binh Khanh

и другие.

Science, Год журнала: 2023, Номер 381(6656), С. 444 - 451

Опубликована: Июль 27, 2023

Developing synthetically useful enzymatic reactions that are not known in biochemistry and organic chemistry is an important challenge biocatalysis. Through the synergistic merger of photoredox catalysis pyridoxal 5'-phosphate (PLP) biocatalysis, we developed a radical biocatalysis approach to prepare valuable noncanonical amino acids, including those bearing stereochemical dyad or triad, without need for protecting groups. Using engineered PLP enzymes, either enantiomeric product could be produced biocatalyst-controlled fashion. Synergistic

Язык: Английский

Процитировано

77
Electrochemical radical-polar crossover: a radical approach to polar chemistry DOI

Zhoumei Tan,

Haonan Zhang, Kun Xu

и другие.

Science China Chemistry, Год журнала: 2023, Номер 67(2), С. 450 - 470

Опубликована: Ноя. 3, 2023

Язык: Английский

Процитировано

50
Photocatalyzed Borylcyclopropanation of Alkenes with a (Diborylmethyl)iodide Reagent DOI Creative Commons
Jiefeng Hu, Man Tang, Jing Wang

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Авг. 2, 2023

Cyclopropane skeletons play a prominent role in the development of organic synthesis and pharmaceutical chemistry. Herein, we report design stable, multifunctional (diborylmethyl)iodide reagent (CHI(Bpin)2 ) for photoinduced cyclopropanation alkenes, providing an array 1,2-substituted cyclopropylboronates good yields. This α-haloboronic ester can be readily synthesized on multigram scale from commercially available starting materials. Furthermore, protocol displays high chemo- diastereoselectivity, excellent functional-group tolerance, allows late-stage borylcyclopropanation complex molecules. Mechanistic studies reveal that proceeds through radical addition/polar cyclization pathway mediated by photocatalyst fac-Ir(ppy)3 visible light.

Язык: Английский

Процитировано

34
Electrochemical generation of aryl radicals from organoboron reagents enabled by pulsed electrosynthesis DOI Creative Commons
Maxime Boudjelel, Jessica Zhong, Lorenzo Ballerini

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(31)

Опубликована: Май 16, 2024

Aryl radicals play a pivotal role as reactive intermediates in chemical synthesis, commonly arising from aryl halides and diazo compounds. Expanding the repertoire of sources for radical generation to include abundant stable organoboron reagents would significantly advance chemistry broaden their reactivity profile. While traditional approaches utilize stoichiometric oxidants or photocatalysis generate these reagents, electrochemical conditions have been largely underexplored. Through rigorous mechanistic investigations, we identified fundamental challenges hindering generation. In addition high oxidation potentials aromatic compounds, electrode passivation through grafting, homocoupling radicals, decomposition issues were identified. We demonstrate that pulsed electrosynthesis enables selective efficient by mitigating challenges. Our discoveries facilitated development first conversion potassium trifluoroborate salts into C-P bonds. This sustainable straightforward oxidative approach exhibited broad substrate scope, accommodating various heterocycles chlorides, typical substrates transition-metal catalyzed cross-coupling reactions. Furthermore, extended this methodology form C-Se, C-Te, C-S bonds, showcasing its versatility potential bond formation processes.

Язык: Английский

Процитировано

10
Late-Stage Isotopic Exchange of Primary Amines DOI
Julia R. Dorsheimer, Tomislav Rovis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(44), С. 24367 - 24374

Опубликована: Окт. 27, 2023

Stable isotopes such as 2H, 13C, and 15N have important applications in chemistry drug discovery. Late-stage incorporation of uncommon via isotopic exchange allows for the direct conversion complex molecules into their valuable isotopologues without requiring a de novo synthesis. While synthetic methods exist hydrogen carbon atoms less abundant isotopes, corresponding method accessing 15N-primary amines from naturally occurring 14N-analogues has not yet been disclosed. We report an approach to access 15N-labeled primary late-stage using simple benzophenone imine source. By activating α-1 α-2° Katritzky pyridinium salts α-3° redox-active imines, we can engage alkyl deaminative amination. The imines proceed radical-polar crossover mechanism, whereas are engaged copper catalysis electron donor–acceptor complex. is general variety amines, including multiple compounds, results complete selective labeling.

Язык: Английский

Процитировано

20
Diverse Synthesis of (Thio)ethers and (Thio)esters Using Halodiborylmethane as a Transformable C1 Building Block DOI
Chiwon Hwang,

Yunhui Jang,

Yongsuk Jung

и другие.

Organic Letters, Год журнала: 2024, Номер 26(33), С. 7010 - 7014

Опубликована: Авг. 8, 2024

The development of effective strategies to forge C–O and C–S bonds in diverse chemical spaces is considerable interest synthetic organic chemistry. Herein we report a versatile approach for the modular synthesis structurally (thio)ethers (thio)esters via homologative coupling α-halodiborylmethane followed by transformation introduced diborylmethyl group. This method accommodates wide array oxygen- sulfur-containing molecules, including biologically active compounds. initial exhibits broad substrate scope, while subsequent diversification moiety enables access various structural motifs through deborylative alkylation, Zweifel olefination, boron-Wittig reaction. protocol efficiently generates diversely functionalized (thio)esters, expanding toolkit accessing relevant scaffolds.

Язык: Английский

Процитировано

7
Synthesis of tertiary alkylphosphonate oligonucleotides through light-driven radical-polar crossover reactions DOI Creative Commons

Kenji Ota,

Kazunori Nagao, Dai Hata

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 31, 2023

Chemical modification of nucleotides can improve the metabolic stability and target specificity oligonucleotide therapeutics, alkylphosphonates have been employed as charge-neutral replacements for naturally-occurring phosphodiester backbones in these compounds. However, at present, alkyl moieties that be attached to phosphorus atoms compounds are limited methyl groups or primary/secondary alkyls, such alkylphosphonate degrade during synthesis. The present work demonstrates tertiary alkylation phosphites bearing two 2'-deoxynuclosides. This process utilizes a carbocation generated via light-driven radical-polar crossover mechanism. protocol provides structures difficult synthesize using existing methods. conversion species oligonucleotides having linkages through phosphoramidite-based approach was also confirmed this study.

Язык: Английский

Процитировано

14
Electrochemically Enabled Intramolecular Amino- and Oxysulfonylation of Alkenes with Sodium Sulfinates to Access Sulfonylated Saturated Heterocycles DOI

Xue‐Qing Mou,

Liang-Chen Ren,

Min Wang

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(5), С. 3238 - 3253

Опубликована: Фев. 22, 2023

A practical and efficient electrochemical intramolecular amino- or oxysulfonylation of internal alkenes equipped with pendant nitrogen oxygen-centered nucleophiles sodium sulfinate was developed. Under undivided electrolytic cell conditions, a variety sulfonylated N-heterocycles O-heterocycles, such as tetrahydrofurans, tetrahydropyrans, oxepanes, tetrahydropyrroles, piperidines, δ-valerolactones, etc., were efficiently prepared from easily accessible unsaturated alcohols, carboxylic acids, N-tosyl amines without the need for additional metal exogenous oxidant. The robust transformation features excellent redox economy, high diastereoselectivity, broad substrate specificity, which provide general access to sulfone-containing heterocycles would facilitate related synthetic biological studies based on this electrosynthesis.

Язык: Английский

Процитировано

11
Electrochemical synthesis and transformation of organoboron compounds DOI

Chunyu Yin,

Shuai Tang,

Jiatong Mei

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(13), С. 3361 - 3377

Опубликована: Янв. 1, 2023

This review highlights the recent advances in both electrochemical borylation and hydroboration to synthesize organoboron compounds transformation of construct carbon–carbon carbon–heteroatom bonds.

Язык: Английский

Процитировано

11
Electrochemistry-Enabled C-Heteroatom Bond Formation of Alkyl Germanes DOI

Markus D. Schoetz,

Kristina Deckers,

Gurdeep Singh

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21257 - 21263

Опубликована: Июль 26, 2024

Because of their robustness and orthogonal reactivity features, alkyl germanes bear significant potential as functional handles for the construction C(sp3)-rich scaffolds, especially in context modular synthetic approaches. However, to date, only radical-based has been accessible from these handles, which limits types possible decorations. Here, we describe first general C(sp3)–heteroatom bond formation (−GeEt3) by leveraging electrochemistry unlock polar reactivity. This approach allowed us couple C(sp3)–GeEt3 with a variety nucleophiles construct ethers, esters, amines, amides, sulfonamides, sulfides, well C–P, C–F, C–C bonds. The compatibility electrochemical strategy C1 motif was also showcased, involving sequential functionalization Cl, Bpin, ultimately GeEt3 via electrochemistry.

Язык: Английский

Процитировано

4