Synthesis of Water-Tolerant Indium Homoenolate in Aqueous Media and Its Application in the Synthesis of 1,4-Dicarbonyl Compounds via Palladium-Catalyzed Coupling with Acid Chloride

Shen, Zhi‐Liang; Goh, Kelvin Kau Kiat; Cheong, Hao‐Lun; Wong, Chee How; Lai, Yin-Chang; Ming, Yang; Loh, Teck‐Peng

doi:10.1021/ja106925f

Cited by 101 publications

(30 citation statements)

References 90 publications

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“…Indium can also be used to generate isolable carbon‐bound homoenolates. In 2010, Loh showed that treatment of vinyl ketones 67 with indium metal in the presence of indium(III) chloride gives the corresponding indium homoenolate 68 (Scheme ) . Not only are these indium homoenolates water‐stable, but they were shown to be viable in palladium‐catalyzed cross‐coupling with acyl chlorides and, in a later report, with aryl halides, making indium reagents 68 easy‐to‐access and synthetically useful homoenolates.…”

Section: Synthesis Of Homoenolatesmentioning

confidence: 99%

Modern Developments in the Chemistry of Homoenolates

Mills

Rousseaux

2018

Eur J Org Chem

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Homoenolates are unique synthetic intermediates which display umpolung reactivity. Homoenolates and homoenolate equivalents like cyclopropanols have seen a recent surge in popularity due to their particular utility for accessing β‐functionalized carbonyl derivatives. This popularity has been enabled by the development of protocols for facile access to cyclopropanols and homoenolates from a variety of readily available starting materials. This microreview will highlight common strategies for generating cyclopropanols and metal homoenolates, as well as procedures for homoenolate functionalization, with a particular emphasis on protocols that have appeared after 2003. As an amphoteric molecule, two main reactivity modes have been established: the homoenolate reacts as a carbon nucleophile for β‐functionalization reactions and/or as a carbonyl electrophile, a strategy which has only emerged in the past few years. This microreview will highlight the use of homoenolates as convenient intermediates for accessing especially challenging motifs. The use of homoenolate chemistry in the context of natural product and pharmaceutical synthesis will also be presented.

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Section: Synthesis Of Homoenolatesmentioning

confidence: 99%

Modern Developments in the Chemistry of Homoenolates

Mills

Rousseaux

2018

Eur J Org Chem

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“…Azedolysis of α,β‐epoxy carboxylic acid with NaN 3 , [24] Polymerization, [25] cyclisation, [26] ring opening reaction of chalcone epoxides with indole and pyrrole [27] are the most important reactions in organic synthesis promoted by InCl 3 . On the basis of environmental consideration, InCl 3 alone and In/InCl 3 system applied in aqueous media for the synthesis of fused pyrimidines and pyrazoles [28] and indium homoenolate (organoindium complex) [29] respectively. Moreover, InCl 3 can be recycled after the synthesis of isatin N ‐ribonucleosides [30] from N ‐phenylribosylamines and diethyl oxalate under microwave irradiation.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances of Indium(III) Chloride Catalyzed Reactions in Organic Synthesis

Datta

2021

ChemistrySelect

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This review summarizes recent advances of indium trichloride catalyzed synthesis of different organic compounds. It is obvious that InCl3 co‐ordinates with C−C and/or C‐heteroatom multiple bonds and thereby makes them very prone to nucleophilic attack to form a new bond. This Lewis acid catalyst also activates oxiranes to produce aldehydes. Multicomponent synthesis including C−C bond formation reaction and construction of N, O and S‐containing heterocycles are discussed in organic solvents as well as in water. This article highlights recent developments and application of indium(III) chloride as a catalyst in organic synthesis from 2015 to 2020. The mechanism of few important reactions is discussed in detail which will be very useful for the readers.

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“…Consequently, numerous multistep approaches to unsymmetrical 1,4-dicarbonyl compounds involving, e.g., S N 2-type displacements [ 1 ] or highly functionalized substrates such as β-ketoesters [ 2 – 3 ] or β-ketosulfones [ 4 ] have been developed. Recently, Loh reported the palladium-catalyzed coupling of an acid chloride with premade isolable indium homoenolates (In(CH 2 CHRC=OR') 2 ), 1.2 equiv relative to the acid chloride) to give the corresponding 1,4-diketones [ 5 ]. Yet the direct coupling of two enolates is inarguably the shortest and most direct path to 1,4-dicarbonyl compounds.…”

Section: Introductionmentioning

confidence: 99%

Cross-coupling of dissimilar ketone enolates via enolonium species to afford non-symmetrical 1,4-diketones

Parida¹,

Pathe²,

Maksymenko³

et al. 2018

Beilstein J. Org. Chem.

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Due to their closely matched reactivity, the coupling of two dissimilar ketone enolates to form a 1,4-diketone remains a challenge in organic synthesis. We herein report that umpolung of a ketone trimethylsilyl enol ether (1 equiv) to form a discrete enolonium species, followed by addition of as little as 1.2–1.4 equivalents of a second trimethylsilyl enol ether, provides an attractive solution to this problem. A wide array of enolates may be used to form the 1,4-diketone products in 38 to 74% yield. Due to the use of two TMS enol ethers as precursors, an optimization of the cross-coupling should include investigating the order of addition.

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Synthesis of Water-Tolerant Indium Homoenolate in Aqueous Media and Its Application in the Synthesis of 1,4-Dicarbonyl Compounds via Palladium-Catalyzed Coupling with Acid Chloride

Cited by 101 publications

References 90 publications

Modern Developments in the Chemistry of Homoenolates

Modern Developments in the Chemistry of Homoenolates

Recent Advances of Indium(III) Chloride Catalyzed Reactions in Organic Synthesis

Cross-coupling of dissimilar ketone enolates via enolonium species to afford non-symmetrical 1,4-diketones

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