HAT lessons help hydrogen hop, skip, and jump DOI
Sarah R. Buzsaki,

Kang‐Jie Bian,

Julian G. West

и другие.

Trends in Chemistry, Год журнала: 2022, Номер 4(12), С. 1062 - 1064

Опубликована: Сен. 20, 2022

Язык: Английский

Metallaphotoredox catalysis for sp3C–H functionalizations through hydrogen atom transfer (HAT) DOI
Jingchang Zhang, Magnus Rueping

Chemical Society Reviews, Год журнала: 2023, Номер 52(12), С. 4099 - 4120

Опубликована: Янв. 1, 2023

sp 3 C–H functionalizations under the combination of photocatalytic HAT and transition metal catalysis.

Язык: Английский

Процитировано

98

Radical Polarity DOI
Jacob J. A. Garwood, Andrew D. Chen, David A. Nagib

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Окт. 3, 2024

The polarity of a radical intermediate profoundly impacts its reactivity and selectivity. To quantify this influence predict effects, the electrophilicity/nucleophilicity >500 radicals has been calculated. This database open-shell species entails frequently encountered synthetic intermediates, including centered at sp

Язык: Английский

Процитировано

45

Enhanced Excited-State Hydricity of Pd–H Allows for Unusual Head-to-Tail Hydroalkenylation of Alkenes DOI
Sumon Sarkar, Soumen Ghosh, Daria Kurandina

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(22), С. 12224 - 12232

Опубликована: Май 24, 2023

Photoinduced enhancement of hydricity palladium hydride species enables unprecedented addition-like (“hydridic”) hydropalladation electron-deficient alkenes, which allows for chemoselective head-to-tail cross-hydroalkenylation and electron-rich alkenes. This mild general protocol works with a wide range densely functionalized complex Notably, this approach also highly challenging cross-dimerization electronically diverse vinyl arenes heteroarenes.

Язык: Английский

Процитировано

31

Cooperative Fe/Co-Catalyzed Remote Desaturation for the Synthesis of Unsaturated Amide Derivatives DOI
Yanjun Wan, Emmanuel Ramírez,

Ayzia Ford

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4985 - 4992

Опубликована: Фев. 6, 2024

Unsaturated amides represent common functional groups found in natural products and bioactive molecules serve as versatile synthetic building blocks. Here, we report an iron(II)/cobalt(II) dual catalytic system for the syntheses of distally unsaturated amide derivatives. The transformation proceeds through iron nitrenoid-mediated 1,5-hydrogen atom transfer (1,5-HAT) mechanism. Subsequently, radical intermediate undergoes hydrogen abstraction from vicinal methylene by a cobaloxime catalyst, efficiently yielding β,γ- or γ,δ-unsaturated derivatives under mild conditions. efficiency Co-mediated HAT can be tuned varying different auxiliaries, highlighting generality this protocol. Remarkably, desaturation protocol is also amenable to practical scalability, enabling synthesis carbamates ureas, which readily converted into various valuable molecules.

Язык: Английский

Процитировано

7

Synthesis of non-canonical amino acids through dehydrogenative tailoring DOI
Xin Gu,

Yu‐An Zhang,

Shuo Zhang

и другие.

Nature, Год журнала: 2024, Номер 634(8033), С. 352 - 358

Опубликована: Авг. 29, 2024

Язык: Английский

Процитировано

7

Directed Photochemically Mediated Nickel-Catalyzed (Hetero)arylation of Aliphatic C–H Bonds DOI

R. Thomas Simons,

Meganathan Nandakumar, Kitae Kwon

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 3882 - 3890

Опубликована: Фев. 13, 2023

Site-selective functionalization of unactivated C(sp3)–H centers is challenging because the ubiquity and strength alkyl C–H bonds. Herein, we disclose a position-selective C(sp3)–C(sp2) cross-coupling reaction. This process engages bonds aryl bromides, utilizing catalytic quantities photoredox-capable molecule nickel precatalyst. Using this technology, selective arises owing to 1,6-hydrogen atom transfer (HAT) that guided by pendant alcohol-anchored sulfamate ester. These transformations proceed directly from N–H bonds, in contrast previous directed, radical-mediated, arylation processes, which have relied on prior oxidation reactive nitrogen center reactions with nucleophilic arenes. Moreover, these conditions promote at secondary good yields excellent selectivity.

Язык: Английский

Процитировано

14

Oxidations of Alcohols, Aldehydes, and Diols Using NaBr and Selectfluor DOI
Harshit Joshi, Debobrata Paul, Shyam Sathyamoorthi

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(15), С. 11240 - 11252

Опубликована: Июль 25, 2023

We present protocols for the oxidation of alcohols and aldehydes oxidative cyclization diols which use a combination Selectfluor NaBr. For most substrates, optimal solvent system is 1:1 mixture CH3CN/H2O, but, in select cases, biphasic mixtures EtOAc/H2O or CH2Cl2/H2O are superior. This procedure operationally simple, uses inexpensive readily available reagents, tolerates variety functional groups. Mechanistic studies suggest that active oxidant hypobromous acid, generated by almost instantaneous Br– an aqueous milieu.

Язык: Английский

Процитировано

11

Nitrogenation and Oxygenation of an Unstrained C–C Bond Enabled by the Merger of Visible-Light and Cu-Catalysis DOI
Yu Wang, Huan Meng, Sifan Li

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(4), С. 2402 - 2408

Опубликована: Янв. 31, 2024

Unstrained carbon–carbon bonds are among the most prevalent and inert chemical bonds. Thus, developing synthetic transformations directly from unstrained under mild conditions is ideal yet challenging due to inertness steric hindrance. Here, a visible-light copper-catalyzed azidation etherification of remote C–C bond amines via 1,4-aryl migration have been reported. This redox-neutral protocol shows exquisite site-selectivity, broad scope, good functional group tolerance, transforming C–N C–O at room temperature. Facile derivatizations benzyl azide products into free amines, triazoles, phosphamides highlight potential utility this method for target molecule synthesis medicinal chemistry.

Язык: Английский

Процитировано

4

γ-Amino C(sp3)–H Functionalization of Aliphatic Amines through a Light-Driven Triple Catalysis DOI

Masanari Nakagawa,

Kazunori Nagao, Hirohisa Ohmiya

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(10), С. 8005 - 8012

Опубликована: Май 9, 2024

We report intra- and intermolecular γ-amino C(sp3)–H functionalization of aliphatic amines using a vinylsulfone-based HAT (hydrogen atom transfer) auxiliary triple catalysis, which is composed photoredox, cobalt, Brønsted acid catalysts under visible light irradiation. The process accomplishes four elementary steps: (i) electrophilic carbon-centered radical formation on the via MHAT (metal hydride hydrogen reaction, (ii) generation through 1,6-HAT (iii) single-electron oxidation to carbocation equivalents, (iv) nucleophilic substitution with internal or external nucleophiles. As result, this afforded γ-amino-functionalized products, such as azetidines, 1,3-diamine, 1,3-aminoalcohol derivatives.

Язык: Английский

Процитировано

4

Modifying commodity-relevant unsaturated polymers via Co-catalyzed MHAT DOI

Yun-Nian Yin,

Bang-Sen Zhao,

Han-Yuan Liu

и другие.

Chem, Год журнала: 2024, Номер 10(10), С. 3088 - 3099

Опубликована: Июнь 19, 2024

Язык: Английский

Процитировано

4