A highly efficient method to access unprotected C-3 bifunctional quaternary 3-allyl-3-(amino)oxindoles DOI
Xunbo Lu, Guoling Huang,

Fangpeng Liang

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(17), С. 3547 - 3551

Опубликована: Янв. 1, 2023

A highly efficient Rh(II) catalyzed non-radical protocol to access NH-free C-3 bifunctional oxindoles, which possess 3-allyl and 3-amino simultaneously, was first achieved by employing an intermolecular [2,3]-sigmatropic rearrangement reaction between diazooxindoles tertiary allylic amines. Utilizing readily available allylamines as the nitrogen allyl source concurrently, a wide range of bio-active 3-allyl-3-(amino)oxindoles were obtained in excellent yields under very mild conditions; meanwhile, TON can be up 90 000. Our study addresses gap literature investigating rearrangements ammonium ylides with diazoamides, have been relatively understudied.

Язык: Английский

Borane-catalyzed arylation of aryldiazoacetates withN,N-dialkylanilines DOI
Cheng‐Yu Chen, Jing‐Hao Zhao,

Li-Xue Xiong

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(20), С. 4101 - 4104

Опубликована: Янв. 1, 2022

We report a catalytic Friedel–Crafts type arylation of donor–acceptor diazo compounds with aniline derivatives under metal-free and mild conditions.

Язык: Английский

Процитировано

8

Gold catalyzed efficient preparation of dihydrobenzofuran from 1,3-enyne and phenol DOI
Yujiang Wang, Yuan Zhang, Qiang Zou

и другие.

Chemical Communications, Год журнала: 2021, Номер 57(94), С. 12607 - 12610

Опубликована: Янв. 1, 2021

A gold catalyzed formal intermolecular [2+3] cyclo-coupling of 1,3-enynes with phenols was developed to prepare dihydrobenzofuran derivatives the addition 2,6-dichloropyridine N-oxide, in which, a highly ortho-selective phenol SEAr functionalization achieved by using as α-oxo vinyl carbenoid surrogates.

Язык: Английский

Процитировано

10

Melding of Experiment and Theory Illuminates Mechanisms of Metal-Catalyzed Rearrangements: Computational Approaches and Caveats DOI
Dean J. Tantillo, Croix J. Laconsay

Synthesis, Год журнала: 2021, Номер 53(20), С. 3639 - 3652

Опубликована: Июль 14, 2021

Abstract This review summarizes approaches and caveats in computational modeling of transition-metal-catalyzed sigmatropic rearrangements involving carbene transfer. We highlight contemporary examples combined synthetic theoretical investigations that showcase the synergy achievable by integrating experiment theory. 1 Introduction 2 Mechanistic Models 3 Theoretical Approaches Caveats 3.1 Recommended Computational Tools 3.2 Choice Functional Basis Set 3.3 Conformations Ligand-Binding Modes 3.4 Solvation 4 Synergy Experiment Theory – Case Studies 4.1 Metal-Bound or Free Ylides? 4.2 Paddlewheel Complexes 4.3 No Metal, Just Light 4.4 How To ‘Cope’ with Nonstatistical Dynamic Effects 5 Outlook

Язык: Английский

Процитировано

9

DFT quest for mechanism and stereoselectivity in B(C6F5)3-catalyzed cyclopropanation of alkenes with aryldiazoacetates DOI

Teng Cao,

Caicai Gao,

Alexander M. Kirillov

и другие.

Molecular Catalysis, Год журнала: 2021, Номер 516, С. 111980 - 111980

Опубликована: Ноя. 1, 2021

Язык: Английский

Процитировано

9

The Reactivity of Acceptor-Acceptor Diazo Pyrazolones with Allyl Thioethers under Visible Light: Access to Homoallyl Sulfides, Spiropyrazolones - Pesticide Analogues and Photoflow Synthesis DOI

Onkar S. Bankar,

Chhabi Pal,

Debasish Laha

и другие.

Organic Letters, Год журнала: 2024, Номер 26(43), С. 9191 - 9197

Опубликована: Окт. 23, 2024

The novel reactivity of a less selective and more reactive acceptor-acceptor kind diazo pyrazolone (DIPOL) has been explored under visible light for the first time. We have successfully demonstrated reaction DIPOL different allyl thioethers blue to construct wide variety products including pesticidal analogue exclusively in excellent chemoselectivity good yields. Moreover, possible side emanating from ketene were not observed. This protocol works smoothly an environmentally benign solvent inert free conditions. practicality extended photoflow reaction, also, direct exposure sunlight.

Язык: Английский

Процитировано

1

Site‐Selective Direct γ‐Difunctionalization of Diazoenals: Application to the Synthesis of Enal‐Functionalized Allenes and Furans DOI Open Access
Jagadeesh Kalepu, Bapurao Sudam Lad, Pratap Kumar Mandal

и другие.

Chemistry - An Asian Journal, Год журнала: 2024, Номер unknown

Опубликована: Окт. 23, 2024

A new approach for the synthetically important γ-functionalized enals has been developed. The strategy involves rhodium-catalyzed direct C-C & C-S bond forming site-selective γ-difunctionalization of diazoenals with aryl propargyl sulfides via sulfur ylide [2,3] sigmatropic rearrangement, resulting in highly functionalized γ-allenyl(sulfanyl)enals excellent yield at ambient temperature. This versatile constitutes a viable alternative to remote carbonyl-directed γ-functionalization unmodified which suffer from competitive side reactions. synthetic utility was demonstrated by InCl

Язык: Английский

Процитировано

1

Synthesis of 1,3,5-Trisubstituted 1,2,4-Triazoles Enabled by a Gold-Catalyzed Three-Component Reaction DOI
Howard Díaz‐Salazar,

Carlos M. Ramírez-González,

Miguel A. Rosas-Ortega

и другие.

Tetrahedron, Год журнала: 2024, Номер 168, С. 134358 - 134358

Опубликована: Ноя. 3, 2024

Язык: Английский

Процитировано

1

Photochemistry of 1-Phenyl-1-diazopropane and Its Diazirine Isomer: A CASSCF and MS-CASPT2 Study DOI Creative Commons
Juan Soto

The Journal of Physical Chemistry A, Год журнала: 2022, Номер 126(45), С. 8372 - 8379

Опубликована: Ноя. 6, 2022

In this work, we studied the wavelength (520 or 350 nm) dependence of photochemical decomposition 1-phenyl-1-diazopropane (PDP) and 1-phenyl-1-propyl diazirine (PED) by means high-level ab initio quantum chemical calculations (CASSCF MS-CASPT2) to obtain qualitative quantitative results. It is found that photochemistry PDP governed nonradiative deactivation processes can involve one two S1/S0 conical intersections (CI1 CI2) depending on radiation; CI2 only accessible at shortest wavelength. demonstrated main intermediate titled compounds 1-ethyl-1-phenyl carbene (EPC). Upon irradiation with 520 nm light, always generated in its ground state as closed-shell singlet carbene. contrast, radiation directly decompose into S1 (open shell) N2 when intersection avoided. Once formed state, it experience excited intramolecular proton transfer along a seam crossing (ESIPT-SC) S0 states yield alkene derivative; is, reaction takes places degenerate potential energy surface where electronic have equal energy. addition, EPC absorbs (double excitations); therefore, there another possible route induce well slightly different changing because (when intense enough) decreases amount available generates highly vibrationally carbene; after excitation, deactivate via emission decay through cascade first (S1), ESIPT-SC operative again.

Язык: Английский

Процитировано

6

Rationalization of the mechanism and chemoselectivity of versatile Au-catalyzed reactions of diazoesters with allyl-functionalized sulfides, selenides, amines, or ethers by DFT DOI

Caicai Gao,

Teng Cao,

Alexander M. Kirillov

и другие.

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(21), С. 6053 - 6062

Опубликована: Янв. 1, 2021

The origin of chemoselectivity and the mechanism title reactions were fully rationalized by density functional theory (DFT).

Язык: Английский

Процитировано

7

Metal-Bound or Free Ylides as Reaction Intermediates in Metal-Catalyzed [2,3]-Sigmatropic Rearrangements? It Depends. DOI Creative Commons
Croix J. Laconsay, Dean J. Tantillo

Опубликована: Ноя. 3, 2020

Density functional theory calculations were applied to study four previously published metal-catalyzed [2,3]-rearrangements from onium ylide intermediates, in pursuit of generalizations about when, during these types reactions, catalysts dissociate. Our results corroborate past studies where free mechanisms proposed be operative. Calculations on case predict that the origin metal-catalyst ‘falling off’ (dissociation) can attributed primarily steric bulkiness groups adjacent carbene carbon.

Язык: Английский

Процитировано

6