New Arylaziridinyldifluoroborates: Useful Suzuki–Miyaura Reagents

Luisi, Renzo; Giovine, Arianna; Florio, Saverio

doi:10.1002/chem.200902056

Cited by 15 publications

(7 citation statements)

References 64 publications

(32 reference statements)

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“…Seminal work by Florio and co-workers reported the synthesis of aryl tetra-coordinated difluoroborates and demonstrated their reactivity toward cross-coupling reactions (Scheme a) . Recently, Harrity and co-workers disclosed a benzannulation reaction mediated by difluoroboranes generated in situ that afforded difluoroboryl benzamides in good yield (Scheme b).…”

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confidence: 99%

Route to Air and Moisture Stable β-Difluoroboryl Acrylamides

et al. 2019

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A method for the preparation of air stable difluoroboryl acrylamides is reported. In contrast to the ubiquitous organotrifluoroborate salts, difluoroboryl acrylamides are relatively nonpolar and are readily purified by silica chromatography. Difluoroboryl acrylamides serve as efficient substrates in cross-coupling reactions to afford the corresponding trisubstituted acrylamides in good to excellent yields. The utility of the difluoroboryl group in various chemical transformations is presented.

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confidence: 99%

Route to Air and Moisture Stable β-Difluoroboryl Acrylamides

et al. 2019

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“…With this series of aziridines in hand, and aware that many aziridine alkaloids have antimicrobial activity against selected pathogenic microorganisms [40,41,42,43], we decided to test preliminary all the aziridine derivatives described in this paper for a potential antibacterial and antifungal profile against different bacterial and fungal strains belonging to American Type Culture Collection (ATCC). For the biological evaluation, also the bisaziridines 8a – d and derivatives 9 , 10 were considered (Figure 1) [35].…”

Section: Resultsmentioning

confidence: 99%

“…The synthetic utility of such ortho -lithiated intermediates has been widely demonstrated even in a D o M-cross coupling strategy [34]. As a matter of fact, a new Suzuki-Miyaura reagent, the cyclic aziridinedifluoroborate 2 , has been prepared from the N -methyl-2-phenylaziridine 1 (Scheme 2) [35]. It has been also demonstrated that the cyclic difluoroborate could be obtained only in the lithiation-borylation of 2-arylaziridines, while the use of ortho -lithiated benzylamines 3a , b led to the corresponding trifluorobrates 4a , b (Scheme 2) [35].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Functionalized Arylaziridines as Potential Antimicrobial Agents

et al. 2014

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By using the Suzuki-Miyaura protocol, a simple straightforward synthesis of functionalized 2-arylaziridines has been developed. By means of this synthetic strategy from readily available ortho-, meta-and para-bromophenylaziridines and aryl-or heteroarylboronic acids, new aziridines could be obtained. The cross-coupling reactions occurred without ring opening of the three membered ring. Preliminary results on the antimicrobial activity of the heterosubstituted biaryl compounds have been also included.

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“…The cyclic aziridinedifluoroborates 22, which can be generated from 19-Li by sequential treatment with an alkylborate and potassium bifluoride (KHF 2 ), can be ortho-arylated in a palladiumcatalyzed Suzuki-Miyaura cross coupling reaction to give the ortho-aryl aziridines 23 (Scheme 8). 22 14 15 The aziridine ring directed lithiation of ortho-tolyl aziridine 24 gives the lithiated species 24-Li, which can be quenched with electrophiles to give more functionalized aziridines 25. In particular, the reaction with carbonyl compounds gives ortho-hydroxyalkylated aziridines (with poor diastereoselectivity), which can be convertible into 1-(aminomethyl)-3,4-dihydro-1H-isochromenes 26 (Scheme 9).…”

Section: N-alkyl-substituted Arylaziridinesmentioning

confidence: 99%

Unraveling the Synthetic Utility of the Regio- and Stereoselective Lithiation of Aziridines

Florio

2012

Synthesis

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The chemistry and synthetic utility of lithiated aziridines are discussed. Lithiated aziridines can be easily generated and captured by electrophiles, leading to more highly functionalized derivatives. Nitrogen dynamics and complexation phenomena play crucial roles in determining the regiochemistry of the lithiation process of aziridines and the stereochemistry of the reactions of the resulting lithiated species with electrophiles. Bench experiments combined with spectroscopic investigations and density-functional theory calculations are particularly useful in elucidating the chemistry of aziridines in their carbanionic form and in unraveling new aspects of the chemistry of aziridines.The aziridine structural motif occurs frequently in natural products and in biologically active substances, and aziridines are common intermediates in organic synthesis. 1 Aziridines are readily accessible 2 in enantiomerically enriched forms and they are mainly used as electrophiles, taking advantage of their predictable, highly regioselective, ring-opening reactions with nucleophiles. Studies on lithiated epoxides and aziridines by my group and others have also demonstrated that there are many other less conventional, but nevertheless useful, reactions that these small-ring heterocycles can undergo. Indeed, when treated with strong bases such as lithium amides or organolithiums, aziridines can undergo α-deprotonation at the aziridine ring carbons to form lithiated derivatives that can be captured with an electrophile to give more substituted products. This lithiation-electrophile trapping sequence, which has been named the aziridinyl anion methodology and has been developed over the last twenty years, parallels the oxiranyl anion methodology. [3][4][5][6] Among the methods developed for the generation of aziridinyl anions are tin-lithium exchange in organotin aziridines, desulfinylation of sulfinyl aziridines, desilylation of silylaziridines, and deprotonation of easily available parent aziridines. 4e Of these, the deprotonation of simple and easily available aziridines remains by far the most convenient and efficient method for generating α-aziridinyl anions.

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New Arylaziridinyldifluoroborates: Useful Suzuki–Miyaura Reagents

Cited by 15 publications

References 64 publications

Route to Air and Moisture Stable β-Difluoroboryl Acrylamides

Route to Air and Moisture Stable β-Difluoroboryl Acrylamides

Synthesis of Functionalized Arylaziridines as Potential Antimicrobial Agents

Unraveling the Synthetic Utility of the Regio- and Stereoselective Lithiation of Aziridines

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