Transition-metal-free chemoselective catalytic hydrosilylation of tertiary amides to hemiaminals by Me2SiH2generated from controllable disproportionation of 1,1,3,3-tetramethyldisiloxane DOI
Xiaoyu Wu, Yue Wang, Liqun Yang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1198 - 1205

Published: Jan. 1, 2023

We present a KO t Bu-catalyzed hydrosilylation for the chemoselective reduction of various tertiary amides to hemiaminals. Mechanistic investigations reveal controllable disproportionation TMDS generate distinctive reductant Me 2 SiH .

Language: Английский

Making Full Use of TMSCF3: Deoxygenative Trifluoromethylation/Silylation of Amides DOI
Yuxiao Wang, Shijun Li,

Feng Jiang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19286 - 19294

Published: July 3, 2024

As one of the most powerful trifluoromethylation reagents, (trifluoromethyl)trimethylsilane (TMSCF3) has been widely used for synthesis fluorine-containing molecules. However, to best our knowledge, simultaneous incorporation both TMS- and CF3- groups this reagent onto same carbon products not realized. Herein, we report an unprecedented SmI2/Sm promoted deoxygenative difunctionalization amides with TMSCF3, in which silyl trifluoromethyl are incorporated into final product, yielding α-silyl-α-trifluoromethyl amines high efficiency. Notably, group could be further transformed other functional groups, providing a new method α-quaternary α-CF3-amines.

Language: Английский

Citations

12
Merging SOMO activation with transition metal catalysis: Deoxygenative functionalization of amides to β-aryl amines DOI Creative Commons

Tian Hongjun,

Feng Jiang,

Xiaoming Wang

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(3)

Published: Jan. 17, 2025

Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success (asymmetric) α-functionalization carbonyl compounds. However, examples on the use this mode transformations other functional groups are rare, and combination SOMO with transition metal catalysis is still less explored. In area deoxygenative functionalization amides, intermediates such as iminium ions were often to result formation α-functionalized amines. contrast, direct deoxygenation amides β-functionalized amines highly appealing yet remains scarcely investigated. Here, a arylation aryl halides was developed via multicatalysis iridium/photoredox/nickel/iridium, affording β-aryl high efficiency. The key reaction enamine synergy Ni-catalyzed arylation, which conjunction two compatible Ir-catalyzed reduction processes.

Language: Английский

Citations

1
Asymmetric Deoxygenative Functionalization of Secondary Amides with Vinylpyridines Enabled by a Triple Iridium-Photoredox-Chiral Phosphoric Acid System DOI

Xiyike Deng,

Feng Jiang,

Xiaoming Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2483 - 2488

Published: March 15, 2024

An enantioselective deoxygenative functionalization of secondary amides with vinylpridines is developed by merging relay iridium catalysis and cooperative photoredox-chiral Brønsted acid catalysis, affording a series valuable chiral amines in moderate to good yields enantioselectivities. The intriguing multiple catalytic system invoking triple-catalysis was found be the key success current reactions, which may stimulate further development methodologies for asymmetric transformations amides.

Language: Английский

Citations

4
Synthesis of (–)-Sedacryptine and (–)-Geissman-Waiss Lactone by Applying Methods for the Direct Transformation of Amides DOI
Yanyan Xu,

Yi Ruan,

Jian‐Feng Zheng

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(3), P. 988 - 988

Published: Jan. 1, 2025

Language: Английский

Citations

0
Photo‐induced Desulfurative Processes for Carbon Radical Generation DOI Creative Commons
Lilian Geniller, Marc Taillefer, Florian Jaroschik

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(20)

Published: July 25, 2023

Abstract Thiols constitute an important family among sulfur‐containing compounds, with well‐established applications in various fields ranging from medicine to material science. For instance, thiol residues are good hydrogen donors which reduce radical species biological or chemical processes. However, even though the S−H bond activation of thiols for providing access thiyl radicals has been largely studied, desulfurative processes affording carbon‐based by C−S have less explored. In recent years, photoredox catalysis become prevalent method generation under soft reaction conditions readily available starting materials visible light. this context, studies devoted development photocatalytic procedures aiming at desulfurization derivatives leading new C−H, C−C C‐Het formation reactions. This review will cover synthetic methodologies and strategies photo‐mediated native thiols, thioethers, sulfonium salts xanthates organic compounds. emerging field is especially interesting transformations cysteine peptide derivatives.

Language: Английский

Citations

10
Deoxygenative alkylation of tertiary amides using alkyl iodides under visible light DOI
Feng Zhao,

Feng Jiang,

Xiaoming Wang

et al.

Science China Chemistry, Journal Year: 2022, Volume and Issue: 65(11), P. 2231 - 2237

Published: July 18, 2022

Language: Английский

Citations

15
α-Aminocarbene-Mediated Si–H Insertion: Deoxygenative Silylation of Aromatic Amides with Silanes DOI

Jiwen Jiao,

Yang Wenhan,

Xiaoming Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(1), P. 594 - 601

Published: Dec. 15, 2022

While metal carbene-mediated Si–H insertion reactions have become a powerful strategy to build new C–Si bonds, the utilization of α-aminocarbene intermediates generated from readily available precursors in reaction remains longstanding challenge. Herein, we develop practical and general synthesize α-aminosilanes through deoxygenative cross-coupling amides silanes mediated by Sm/SmI2. Given simplicity versatility, this methodology represents fascinating example for effective inert as organic synthesis.

Language: Английский

Citations

11
Deoxygenative Radical Boration of Inert Amides via a Combination of Relay and Cooperative Catalysis DOI

Feng Jiang,

Jingan Li, Xiaoming Wang

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(35)

Published: April 19, 2023

One of the most challenging tasks in organic synthesis is to develop novel methodologies for rapid construction complex molecules starting from easily available yet inert raw materials. In this context, multi-catalysis strategies have attracted great attention discovery new reactivity profiles that may allow access many difficult or unattainable transformations. So far deoxygenative functionalization ubiquitous amides usually achieved by nucleophilic attack on imine iminium ion intermediate formed via activation C=O bond, and these reagents were often confined C-based nucleophiles, which largely limited diversity resultant amines. Herein, we disclose a combined strategy relay cooperative catalysis with triple iridium-photoredox-organocatalysis system achieve an unprecedented reductive boration amides, affording valuable α-amino boron products are viable building blocks. transformation, Ir-catalyzed semi-reduction successfully incorporated photo-organic catalyzed boryl radical addition, thus delivering corresponding α-boryl amines high efficiency.

Language: Английский

Citations

6
Deoxygenative arylation of secondary amides by merging iridium catalysis with electrochemical radical cross-coupling DOI
Jingan Li,

Youliang He,

Feng Jiang

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(22), P. 9080 - 9085

Published: Jan. 1, 2023

A deoxygenative arylation of amides using aromatic nitriles via merging Ir-catalyzed amide reduction with electrochemistry has been achieved, which may provide an alternative strategy for access to value-added amines from inert amides.

Language: Английский

Citations

6
Iridium‐Catalyzed Reductive (3+2) Annulation of Lactams Enabling the Rapid Total Synthesis of (±)‐Eburnamonine DOI Creative Commons

Yasukazu Sugiyama,

Kento Yamada,

Daiki Kaneko

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(6)

Published: Dec. 13, 2023

A reductive (3+2) annulation of lactams through iridium-catalyzed hydrosilylation and photoredox coupling with α-bromoacetic acid was developed. The the lactam carbonyl group subsequent elimination provide a transient cyclic enamine, which undergoes in one-pot process. developed conditions show high functional-group tolerance N,O-acetals containing quaternary carbon center. resulting undergo variety acid-mediated nucleophilic addition reactions via iminium ions to give substituted amines. sequence including successfully applied four-step total synthesis (±)-eburnamonine.

Language: Английский

Citations

6