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21 Nov 17:16

[ASAP] Cyclopropenium Ions in Catalysis

by Rebecca M. Wilson and Tristan H. Lambert

TOC Graphic

Accounts of Chemical Research

DOI: 10.1021/acs.accounts.2c00546

MRV likes this

08 Nov 10:53

[ASAP] Practical and Facile Access to Bicyclo[3.1.1]heptanes: Potent Bioisosteres of meta-Substituted Benzenes

by Toranosuke Iida, Junichiro Kanazawa, Tadafumi Matsunaga, Kazunori Miyamoto, Keiichi Hirano, and Masanobu Uchiyama

TOC Graphic

Journal of the American Chemical Society

DOI: 10.1021/jacs.2c09733

MRV, Rubén and one other like this

07 Nov 15:56

Excited-State Palladium-Catalyzed α-Selective C1-Ketonylation

by Gaoyuan Zhao, Upasana Mukherjee, Lin Zhou, Jaclyn N. Mauro, Yue Wu, Peng Liu & Ming-Yu Ngai1Department of Chemistry, Institute of Chemical Biology and Drug Discovery, State University of New York at Stony Brook, Stony Brook, New York 117942Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 152603Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260

CCS Chemistry, Volume 5, Issue 1, Page 106-116, January 2023.

Juba Ghouilem likes this

17 Oct 20:16

A broadly applicable quantitative relative reactivity model for nucleophilic aromatic substitution (SNAr) using simple descriptors

Chem. Sci., 2022, 13,12681-12695
DOI: 10.1039/D2SC04041G, Edge Article

Open Access

&nbsp This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

Jingru Lu, Irina Paci, David C. Leitch
A model for S_NAr reactivity is reported, built from relative rate data obtained by competition studies. Based only on molecular descriptors of the electrophile, the model predicts relative reactivity and site selectivity for many complex substrates.
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10 Oct 10:17

Oxidative Cleavage of Alkenes by Photosensitized Nitroarenes

by Tuhin Patra, Thomas Wirth

This article highlights the recent seminal findings on the possibility to use photoexcited nitroarenes as modular and easily dosable reagents which can mimic the reactivity of ozonolysis for the oxidative conversion of alkenyl bonds into carbonyl groups in a highly selective fashion.

Abstract

Oxidative cleavage of alkenes into carbonyl molecules mainly relies on either ozonolysis or Lemieux-Johnson oxidation involving high valent transition metal oxides. Safety, technical concerns and highly oxidizing conditions of both these procedures limited their adoption in streamlined synthesis. Like ozone, photosensitized nitroarenes can deliver similar types of [3+2] cycloaddition products with alkenes through biradical formation and the resulting “N-doped” ozonides can safely be converted to the corresponding carbonyl compounds through hydrolysis. The high prevalence of nitroarenes with diverse electronic and steric profiles combined with the mild oxidizing power allow to modulate site-selectivity and tolerate highly sensitive functional groups ideal for application in complex molecular setup.

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02 Sep 08:59

[ASAP] Metal-Free Photochemical Imino-Alkylation of Alkenes with Bifunctional Oxime Esters

by Jadab Majhi, Roshan K. Dhungana, Ángel Rentería-Gómez, Mohammed Sharique, Longbo Li, Weizhe Dong, Osvaldo Gutierrez, and Gary A. Molander

TOC Graphic

Journal of the American Chemical Society

DOI: 10.1021/jacs.2c07170

M. L. Lepage, MRV and 7 others like this

02 Sep 08:58

[ASAP] Visible-Light Photocatalyzed peri-(3 + 2) Cycloadditions of Quinolines

by Peter Bellotti, Torben Rogge, Fritz Paulus, Ranjini Laskar, Nils Rendel, Jiajia Ma, K. N. Houk, and Frank Glorius

MRV
!

TOC Graphic

Journal of the American Chemical Society

DOI: 10.1021/jacs.2c05687

MRV, Rubén and 9 others like this

02 Sep 08:52

[ASAP] Hydroamination of Unactivated Alkenes with Aliphatic Azides

by Si-Ming Jia, Yi-Hang Huang, Zhan-Lin Wang, Fang-Xu Fan, Bo-Han Fan, Hao-Xiang Sun, Hao Wang, and Fei Wang

TOC Graphic

Journal of the American Chemical Society

DOI: 10.1021/jacs.2c07643

lishuang, 123rliu and 2 others like this

02 Sep 08:50

[ASAP] Ligand Development for Copper-Catalyzed Enantioconvergent Radical Cross-Coupling of Racemic Alkyl Halides

by Xiao-Yang Dong, Zhong-Liang Li, Qiang-Shuai Gu, and Xin-Yuan Liu

TOC Graphic

Journal of the American Chemical Society

DOI: 10.1021/jacs.2c06718

bianmingsioc, MRV and one other like this

25 Aug 09:08

[ASAP] Catalytic Lewis Base Additive Enables Selective Copper-Catalyzed Borylative α‑C–H Allylation of Alicyclic Amines

by Borja Pérez-Saavedra, Álvaro Velasco-Rubio, Eva Rivera-Chao, Jesús A. Varela, Carlos Saá, and Martín Fañanás-Mastral

TOC Graphic

Journal of the American Chemical Society

DOI: 10.1021/jacs.2c07969

Damián, jiarongchen and 2 others like this

18 Aug 07:19

[ASAP] Photoinduced Oxygen Transfer Using Nitroarenes for the Anaerobic Cleavage of Alkenes

by Dan E. Wise, Emma S. Gogarnoiu, Alana D. Duke, Joshua M. Paolillo, Taylor L. Vacala, Waseem A. Hussain, and Marvin Parasram

TOC Graphic

Journal of the American Chemical Society

DOI: 10.1021/jacs.2c05648

MRV, Rubén and 10 others like this

02 Jul 12:56

[ASAP] Synthesis of β‑Polychlorinated Alkynes Enabled by Copper-Catalyzed Multicomponent Reaction

by Qiuzhu Wang, Mengning Wang, Qianhui Wu, Mengtao Ma, and Binlin Zhao

TOC Graphic

Organic Letters

DOI: 10.1021/acs.orglett.2c01755

IIIIIIIIIIIIIIII, MRV likes this

28 Jun 08:12

Progress in Convergent Paired Electrolysis

by Sheng Zhang, Michael Findlater

Recent progress on convergent paired electrolysis has been summarized in this concept article. Four strategies based upon metal catalysis, persistent radical effects, microfluidic chemistry, and alternating current electrolysis are discussed in relation to their underlying mechanisms.

Abstract

Convergent paired electrolysis combines both anodic and cathodic reactions simultaneously in an electrochemical transformation. It provides a highly energy-efficient and divergent approach to conventionally challenging and useful structures. However, the physical separation of the two half-electrode reactions makes it extremely difficult to couple the intermediates arising from the two electrodes. In this concept article, four strategies used in convergent paired electrolysis will be discussed from the perspective of the reaction mechanism: a) metal-catalyzed convergent paired electrolysis, b) convergent paired electrolysis enabled by persistent radical effects, c) microfluidic chemistry applied to convergent paired electrolysis, and d) alternating current electrolysis.

MRV likes this

28 Jun 08:09

[ASAP] A Pyridine-Based Donor–Acceptor Molecule: A Highly Reactive Organophotocatalyst That Enables the Reductive Cleavage of C–Br Bonds through Halogen Bonding

by Natsuki Kato, Takeshi Nanjo, and Yoshiji Takemoto

TOC Graphic

ACS Catalysis

DOI: 10.1021/acscatal.2c02067

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17 Jun 12:10

Iron-catalyzed ring-opening of cyclic carboxylic acids enabled by photoinduced ligand-to-metal charge transfer

Green Chem., 2022, 24,5553-5558
DOI: 10.1039/D2GC01738E, Paper

Jia-Lin Tu, Han Gao, Mengqi Luo, Lulu Zhao, Chao Yang, Lin Guo, Wujiong Xia
A decarboxylative ring-opening reaction of cyclic tertiary carboxylic acids via an iron-catalyzed photoinduced ligand-to-metal charge transfer (LMCT) process is herein reported.
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MRV likes this

15 Jun 13:54

[ASAP] Regio- and Stereoselective Electrochemical Alkylation of Morita–Baylis–Hillman Adducts

by Giulio Bertuzzi, Giada Ombrosi, and Marco Bandini

TOC Graphic

Organic Letters

DOI: 10.1021/acs.orglett.2c01529

MRV and -1 others like this

03 Jun 09:57

[ASAP] Organocatalyzed Cross-Nucleophile Couplings: Umpolung of Catalytic Enamines

by Nomaan M. Rezayee, Johannes N. Lamhauge, and Karl Anker Jrgensen

TOC Graphic

Accounts of Chemical Research

DOI: 10.1021/acs.accounts.2c00149

erlyj2006, MRV and 2 others like this

14 May 15:33

[ASAP] Photoinduced Transition-Metal-Free Chan–Evans–Lam-Type Coupling: Dual Photoexcitation Mode with Halide Anion Effect

by Zijun Zhou, Jeonguk Kweon, Hoimin Jung, Dongwook Kim, Sangwon Seo, and Sukbok Chang

TOC Graphic

Journal of the American Chemical Society

DOI: 10.1021/jacs.2c03343

WCJ-737, Mickael.henrion and one other like this

09 May 17:23

Copper‐Catalyzed Radical Enantioselective Carbo‐Esterification of Styrenes Enabled by a Perfluoroalkylated‐PyBox Ligand

by Zaicheng Nie, Mong-Feng Chiou, Jinfeng Cui, Yanjie Qu, Xiaotao Zhu, Wujun Jian, Haigen Xiong, Yajun Li, Hongli Bao

MRV
.....

Copper-Catalyzed Radical Enantioselective Carbo-Esterification of Styrenes Enabled by a Perfluoroalkylated-PyBox Ligand

The radical enantioselective carbo-esterification of styrenes enabled by a newly developed perfluoroalkylated-PyBox ligand and copper catalysis is reported. Mechanistic studies reveal that this reaction is a rare example of an efficient ligand-decelerated system, in which the ligand decelerates the reaction, but the reaction is still efficient with reduced amounts of ligand.

Abstract

Chiral lactones are found in many natural products. The reaction of simple alkenes with iodoacetic acid is a powerful method to build lactones, but the enantioselective version of this reaction has not been implemented to date. Herein, we report the efficient catalytic radical enantioselective carbo-esterification of styrenes enabled by a newly developed Cu^I-perfluoroalkylated PyBox system. Simple styrenes have been converted to useful chiral lactones, whose synthetic applications are showcased. Mechanistic studies reveal that this reaction is a rare example of an efficient ligand-decelerated system, in which the ligand decelerates the reaction, but the reaction is still efficient with reduced amounts of ligand. This uncommon catalytic system may inspire further consideration of the effect of ligands in asymmetric catalysis.

MRV likes this

09 May 15:38

Para‐Fluorination of Anilides Using Electrochemically Generated Hypervalent Iodoarenes

by Michael Berger, Marola S. Lenhard, Siegfried R Waldvogel

MRV
electrochemical fluorination

Para-Fluorination of Anilides Using Electrochemically Generated Hypervalent Iodoarenes

An electrochemical transformation for the selective para-fluorination of anilides is presented. Herein, anodically generated ArIF2 mediates the conversion of a variety of 20 different anilides in up to 86 % yield. The sustainable and easy to conduct protocol in an ionic-liquid / dicholoromethane mixture represents a promising alternative to conventional reagent mediated synthesis protocol.

Abstract

The para-selective fluorination reaction of anilides using electrochemically generated hypervalent ArIF₂ is reported, with Et₃N ⋅ 5HF serving as fluoride source and as supporting electrolyte. This electrochemical reaction is characterized by a simple set-up, easy scalability and affords a broad variety of fluorinated anilides from easily accessible anilides in good yields up to 86 %.

MRV likes this

09 May 15:36

Catalytic asymmetric Tsuji–Trost α−benzylation reaction of N-unprotected amino acids and benzyl alcohol derivatives

MRV
:nice:

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09 May 08:23

[ASAP] Organocatalytic Asymmetric Dearomatizing Hetero-Diels–Alder Reaction of Nonactivated Arenes

by Kai Li, Shengli Huang, Tianyu Liu, Shiqi Jia, and Hailong Yan

MRV

TOC Graphic

Journal of the American Chemical Society

DOI: 10.1021/jacs.2c01106

MRV, WCJ-737 and 2 others like this

15 Apr 19:21

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

Chem. Soc. Rev., 2022, 51,2313-2382
DOI: 10.1039/D1CS00510C, Review Article

Guglielmo A. Coppola, Serena Pillitteri, Erik V. Van der Eycken, Shu-Li You, Upendra K. Sharma
This review offers an overview of recent synthetic strategies employing photoredox catalysis and electrochemistry in the framework of multicomponent reactions.
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15 Apr 12:23

Metal-free oxoammonium salt-mediated C(sp3)–H oxidative Ugi-azide multicomponent reaction

MRV
LG

Org. Biomol. Chem., 2022, 20,2896-2908
DOI: 10.1039/D2OB00101B, Paper

Niklas Lohmann, Vesna Milovanović, Dariusz G. Piekarski, Olga García Mancheño
A one-pot, oxidative Ugi-azide multicomponent reaction mediated by oxoammonium salts is presented. This method provides a direct access to α-tetrazolo N-heterocycles in excellent yields employing simple NaN₃ as azide source.
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15 Apr 11:48

Silver-promoted dearomative [3+4] cycloaddition of anthranils with α-isocyanoacetates: access to benzodiazepines

MRV
LG

Chem. Commun., 2022, 58,4771-4774
DOI: 10.1039/D2CC00807F, Communication

Rui Shao, Haixia Zhao, Shumin Ding, Lianjie Li, Chen Chen, Jian Wang, Yongjia Shang
We herein reported the first silver-promoted [3+4] cycloaddition of α-isocyanoacetates with anthranils as aromatic Michael accepters. Benzo[d][1,3]diazepinones were accessed under mild conditions through an “oxygen migration” rearrangement process.
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14 Apr 08:24

Cooperative Palladium/Isothiourea Catalyzed Enantioselective Formal (3+2) Cycloaddition of Vinylcyclopropanes and α,β‐Unsaturated Esters

by Jacqueline Bitai, Alastair J. Nimmo, Alexandra M. Z. Slawin, Andrew David Smith

MRV
idée de 2019 non financé par l'ANR....

Cooperative Palladium/Isothiourea Catalyzed Enantioselective Formal (3+2) Cycloaddition of Vinylcyclopropanes and α,β-Unsaturated Esters

Cooperative palladium and isothiourea catalysis allows the formal (3+2) cycloaddition of vinylcyclopropanes and α,β-unsaturated esters to generate functionalized cyclopentanes via an α,β-unsaturated acyl ammonium intermediate with the addition of LiCl crucial to obtain high product diastereo- and enantioselectivity.

Abstract

A protocol for the enantioselective synthesis of substituted vinylcyclopentanes has been realised using cooperative palladium and isothiourea catalysis. Treatment of vinylcyclopropanes with Pd(PPh₃)₄ generates a zwitterionic π-allyl palladium intermediate that intercepts a catalytically generated α,β-unsaturated acyl ammonium species prepared from the corresponding α,β-unsaturated para-nitrophenyl ester and the isothiourea (R)-BTM. Intermolecular formal (3+2) cycloaddition between these reactive intermediates generates functionalised cyclopentanes in generally good yields and excellent diastereo- and enantiocontrol (up to >95 : 5 dr, 97 : 3 er), with the use of LiCl as an additive proving essential for optimal stereocontrol. To the best of our knowledge a dual transition metal/organocatalytic process involving α,β-unsaturated acyl ammonium intermediates has not been demonstrated previously.

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14 Apr 08:18