HFIP in Organic Synthesis

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(15), P. 12544 - 12747

Published: July 17, 2022

1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability stabilize ionic species, transfer protons, and engage range of other intermolecular interactions. The use this exponentially increased the past decade become choice some areas, such as C–H functionalization chemistry. In review, following brief history HFIP an overview physical properties, literature examples reactions using or additive are presented, emphasizing effect each reaction.

Language: Английский

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N‐Heterocyclic Carbene/Copper Cooperative Catalysis for the Asymmetric Synthesis of Spirooxindoles

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(35), P. 12190 - 12194

Published: June 28, 2019

Highly enantioselective [3+3] and [3+4] annulations of isatin-derived enals with ethynylethylene carbonates ethynyl benzoxazinanones are enabled by NHC/cooper cooperative catalysis, leading to a big library spirooxindole derivatives in high structural diversity enantioselectivity (up 99 % ee). Both reactions represent nicely synergistic integration NHC copper which both catalysts activate the substrates chiral perfectly controls stereochemistry.

Language: Английский

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Synthesis and applications of sodium sulfinates (RSO₂Na): a powerful building block for the synthesis of organosulfur compounds

RSC Advances, Journal Year: 2021, Volume and Issue: 11(16), P. 9130 - 9221

Published: Jan. 1, 2021

This review provides a unique and comprehensive overview of sodium sulfinates for synthesizing many valuable sulfur-containing compounds, such as thiosulfonates, sulfonamides, sulfides, sulfones, allyl vinyl sulfones β-keto sulfones.

Language: Английский

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Recent Advances in the Catalytic Synthesis of Arylsulfonyl Compounds

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(7), P. 4169 - 4204

Published: March 19, 2021

Arylsulfonyl compounds are among the most important in pharmaceutical and medicinal chemistry. Hence, a wide variety of sulfonylation methods have been reported recently. This review summarizes arylsulfonylation methodologies developed last 5 years includes two major categories. The first entails direct second multicomponent arylsulfonylation. In arylsulfonylation, arylsulfonyl reagents react with C–H activated compounds, alkynes, alkenes through coupling or addition reactions. reactions, arylation various substrates sulfur dioxide surrogates, such as DABSO, Na2S2O5, K2S2O5. hydrazides, aryl boronic acids, silanes, halides widely employed that surrogates to generate an source, ensuing reactions proceed via pathways analogous those

Language: Английский

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Enantioselective propargylic amination and related tandem sequences to α-tertiary ethynylamines and azacycles

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(4), P. 521 - 532

Published: March 19, 2024

Language: Английский

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Copper-Catalyzed Asymmetric Yne-Allylic Substitution Using Electron-Rich Arenes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2746 - 2757

Published: Feb. 7, 2024

Remote stereocontrol in transition-metal catalysis is a challenging but interesting research topic. In this work, we achieved copper-catalyzed asymmetric yne-allylic substitution using electron-rich arenes and acyclic carbonates through remote enantioselectivity control. The reaction delivers variety of enantioenriched products that contain diverse set valuable moieties, such as conjugated enynes, indoles, indolizines, allenes, dihydrofurans, which are widely used organic synthesis act key units bioactive molecules natural products. synthetic value protocol has been demonstrated series further transformations, mechanistic studies have conducted to gain more insight into the reaction.

Language: Английский

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Palladium-Catalyzed Regio- and Enantioselective Hydrosulfonylation of 1,3-Dienes with Sulfinic Acids: Scope, Mechanism, and Origin of Selectivity

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(37), P. 15860 - 15869

Published: Aug. 19, 2020

Chiral sulfones are important structural motifs in organic synthesis because of their widespread use pharmaceutical chemistry. In particular, chiral allylic have drawn particular interest synthetic utility. However, enantioselective 1,3-disubstituted unsymmetrical remains a challenge. this article, we report protocol for (R)-DTBM-Segphos/Pd-catalyzed regio- and hydrosulfonylation 1,3-dienes with sulfinic acids, which provides atom- step-economical access to sulfones. The reaction occurs under mild conditions has broad substrate scope. Combined experimental computational studies suggest that the is initiated by ligand-to-ligand hydrogen transfer followed C–S bond reductive elimination via six-membered transition state. Steric repulsion between olefinic C–H tert-butyl group (R)-DTBM-Segphos was found be key factor enantiocontrol.

Language: Английский

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An Update of Transition Metal-Catalyzed Decarboxylative Transformations of Cyclic Carbonates and Carbamates

Molecules, Journal Year: 2019, Volume and Issue: 24(21), P. 3930 - 3930

Published: Oct. 31, 2019

Functionalized cyclic organic carbonates and carbamates are frequently used in a number of transition metal-catalyzed decarboxylative reactions for the construction interesting molecules. These transformations have attracted more research attention recent years mainly due to their advantages less waste generation versatile reactivities. On basis previous reviews on this hot topic, present review will focus development functionalized last two years.

Language: Английский

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Regio‐ and Enantioselective Synthesis of Sulfone‐Bearing Quaternary Carbon Stereocenters by Pd‐Catalyzed Allylic Substitution

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(3), P. 1340 - 1345

Published: Sept. 10, 2019

Abstract Chiral sulfones are of great importance in medicinal chemistry and chemical synthesis. Efficient methods for preparing enantiomerically enriched sulfone‐containing molecules can therefore be significant value; such methods, however, uncommon. Herein, we report the first general palladium‐catalyzed sulfonylation vinyl cyclic carbonates with sodium sulfinates. A series tertiary allylic were synthesized good yields excellent enantiomeric ratios. Both aliphatic‐ aryl‐substituted suitable reactants results. This reaction features broad substrates scope, readily available starting materials, regio‐ enantioselectivity, synthesis sulfone‐bearing quaternary carbon stereocenters. Through geranyl derived carbonate 1 h , achieve formal total (+)‐agelasidine A.

Language: Английский

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Palladium‐Catalyzed Asymmetric Hydrosulfonylation of 1,3‐Dienes with Sulfonyl Hydrazides

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(6), P. 2948 - 2951

Published: Oct. 23, 2020

A highly enantio- and regioselective hydrosulfonylation of 1,3-dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful allylic sulfones. Mechanistic studies suggest that the proceeds through formation allyl hydrazine intermediate subsequent rearrangement sulfone product. transformation product is enantioselectivity-determining step.

Language: Английский

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