Recent Developments in Enantioselective Organocatalytic Cascade Reactions for the Construction of Halogenated Ring Systems DOI
Ana Maria Faísca Phillips, Armando J. L. Pombeiro

European Journal of Organic Chemistry, Год журнала: 2021, Номер 2021(29), С. 3938 - 3969

Опубликована: Июнь 7, 2021

Abstract Chiral halogenated substances have many applications in pharmaceuticals, agrochemicals, and materials, such as polymers, liquid crystals intermediates synthesis. The presence of a halogen atom molecule can large effect its properties; for instance, halogens are used drugs to improve lipophilicity, membrane permeability absorption, even the blood‐brain barrier permeability. As highlighted this review, there nowadays range highly selective, versatile halogenating reagents, electrophilic, nucleophilic or radical nature, which operate under mild conditions, allowing late‐stage functionalization complex molecules cascade reactions. Recent developments organocatalyst design revealed novel Cinchona alkaloids derivatives, chiral phosphoric acids, amines, phosphines several bifunctional catalysts, mostly thiourea‐ squaramide‐based, introduced chirality, with high levels enantio‐ diastereoselection, formation one multiple centers single synthetic operation, shown. In review we survey literature published field from 2014 2020.

Язык: Английский

Recent Advances in Catalytic Asymmetric Syntheses of Functionalized Heterocycles via Halogenation/Chalcogenation of Carbon‐Carbon Unsaturated Bonds DOI
Shengshu Liu,

Bing‐Qian Zhang,

Wen‐Ying Xiao

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(23), С. 3974 - 4005

Опубликована: Окт. 20, 2022

Abstract Halogen (fluorine, chlorine, bromine, iodine) or chalcogen (sulfur, selenium)‐containing heterocycles are widely recognized as key building blocks in many natural products and bioactive targets. Catalytic asymmetric halogenation/chalcogenation of carbon‐carbon unsaturated bonds via onium ion transformations efficient methods to obtain diverse chiral heterocyclic backbones. In the past few years, catalytic enantioselective versions halo/thio/seleno‐functionalizations with various halogen electrophiles have experienced constant development. This review highlights those advances preparing functionalized promoted by organocatalysts metal‐based catalysts. magnified image

Язык: Английский

Процитировано

27

Catalytic alkene skeletal modification for the construction of fluorinated tertiary stereocenters DOI Creative Commons
Liyin Jiang, Pau Sarró, Wei Jie Teo

и другие.

Chemical Science, Год журнала: 2022, Номер 13(15), С. 4327 - 4333

Опубликована: Янв. 1, 2022

We report a previously unknown disconnection approach to valuable fluorinated tertiary stereocenters based on the skeletal modification of 1,1-disubstituted alkenes by Rh-catalyzed carbyne transfer.

Язык: Английский

Процитировано

25

Catalytic Homologation‐Allylboration Sequence for Diastereo‐ and Enantioselective Synthesis of Densely Functionalized β‐Fluorohydrins with Tertiary Fluoride Stereocenters DOI Creative Commons
Qiang Wang,

Lars Eriksson,

Kálmán J. Szabó

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(19)

Опубликована: Март 8, 2023

Homologation of trisubstituted fluoroalkenes followed by allylboration aldehyde, ketone and imine substrates is suitable for synthesis β-fluorohydrin amine products. In the presence (R)-iodo-BINOL catalyst enantioselectivities up to 99 % can be achieved formation a single stereoisomer with adjacent stereocenters, which one tertiary C-F center.

Язык: Английский

Процитировано

13

Catalytic stereoselective synthesis involving hypervalent iodine-based chiral auxiliaries DOI

Samata E. Shetgaonkar,

Fateh V. Singh

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(20), С. 4163 - 4180

Опубликована: Янв. 1, 2023

A number of organic transformations have been achieved using hypervalent iodine reagents under mild reaction conditions. The use these as chiral organocatalyst exhibited highly selective asymmetric reactions.

Язык: Английский

Процитировано

13

Asymmetric hydrogenation of γ‐branched allylamines for the efficient synthesis of γ‐chirogenic amines DOI Creative Commons
Jian Zhang, Tiantian Chen, Yuanhao Wang

и другие.

Natural Sciences, Год журнала: 2021, Номер 1(2)

Опубликована: Авг. 5, 2021

Abstract The efficient construction of γ ‐chirogenic amines has been realized via asymmetric hydrogenation ‐branched N ‐phthaloyl allylamines by using a bisphosphine‐Rh catalyst bearing large bite angle. desired products possessing different ‐substituents were obtained in quantitative yields and with excellent enantioselectivities (up to >99% ee). This protocol provides practical method for the preparation amine derivatives such as famous antidepressant drug Fluoxetine 50000 S/C). mechanistic calculations show an unusual P‐Rh‐P trans ‐chelating pattern weak interaction‐promoted activation mode which are completely from traditional cis coordination‐promoted metal‐catalyzed hydrogenations. Key points Novel methodology was developed synthesis γ‐chirogenic amines. New synthetic route well‐known Fluoxetine. Unusual mechanism information found bidentate bisphosphine‐Rh‐catalyzed hydrogenation.

Язык: Английский

Процитировано

24

The applications of catalytic asymmetric halocyclization in natural product synthesis DOI

Jiahang Yan,

Zhiqiang Zhou,

Qiaoqiao He

и другие.

Organic Chemistry Frontiers, Год журнала: 2021, Номер 9(2), С. 499 - 516

Опубликована: Ноя. 18, 2021

Catalytic asymmetric halocyclization of olefinic substrate has evolved rapidly and been well utilized as a practical strategy for constructing enantioenriched cyclic skeletons in natural product synthesis.

Язык: Английский

Процитировано

24

Catalytic, Regioselective 1,4‐Fluorodifunctionalization of Dienes DOI Creative Commons

You‐Jie Yu,

Michael Schäfer,

Constantin G. Daniliuc

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(1)

Опубликована: Ноя. 8, 2022

Abstract A catalysis‐based regioselective 1,4‐fluorofunctionalization of trifluoromethyl substituted 1,3‐dienes has been developed to access compact, highly functionalized products. The process allows E , Z ‐mixed dienes be processed a single ‐alkene isomer, and leverages an inexpensive operationally convenient I(I)/I(III) catalysis platform. first example catalytic 1,4‐difluorination is disclosed subsequently evolved enable 1,4‐hetero‐difunctionalization, which δ‐fluoro‐alcohol amine derivatives forged in operation. protocol compatible with variety nucleophiles including fluoride, nitriles, carboxylic acids, alcohols even water thereby allowing products, stereocenter bearing both C(sp 3 )−F )−CF groups, generated rapidly. Scalability (up mmol), facile post‐reaction modifications are demonstrated underscore the utility method expanding organofluorine chemical space.

Язык: Английский

Процитировано

18

Recent advances in catalytic asymmetric haloamination and haloetherification of alkenes DOI
Chuan‐Zhi Yao,

Xue‐Qin Tu,

Hua‐Jie Jiang

и другие.

Tetrahedron Letters, Год журнала: 2023, Номер 126, С. 154639 - 154639

Опубликована: Июль 5, 2023

Язык: Английский

Процитировано

11

Copper-catalyzed [3 + 2]-cycloaddition of α-halonitroalkenes with azomethine ylides: facile synthesis of multisubstituted pyrrolidines and pyrroles DOI
Vladimir Motornov, Andrey A. Tabolin, Yulia V. Nelyubina

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2021, Номер 19(15), С. 3413 - 3427

Опубликована: Янв. 1, 2021

An approach to multisubstituted pyrrolidines, pyrrolines and pyrroles is developed based on [3 + 2]-cycloaddition of α-halo (F, Cl, Br) nitroalkenes.

Язык: Английский

Процитировано

23

Determination of the Hammett Acidity of HF/Base Reagents DOI

Mélissa Longuet,

Kassandra Vitse,

Agnès Martin‐Mingot

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(17), С. 12167 - 12173

Опубликована: Апрель 16, 2024

Harnessing the acidity of HF/base reagents is paramount importance to improve efficiency and selectivity fluorination reactions. Yet, no general method has been reported evaluate their acidic properties, experimental designs are still relying on a trial-and-error approach. We report new based

Язык: Английский

Процитировано

3