Mild and Phosphine-Free Iron-Catalyzed Cross-Coupling of Nonactivated Secondary Alkyl Halides with Alkynyl Grignard Reagents

Cheung, Chi Wai; Ren, Peng; Hu, Xile

doi:10.1021/ol501087m

Cited by 85 publications

(53 citation statements)

References 60 publications

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“…4 A 1 L round-bottom flask equipped with a Teflon-coated magnetic stir bar was charged with triphenylphosphine (1.4 equiv), imidazole (1.4 equiv), and dichloromethane (~300 mL). The reaction mixture was stirred at room temperature until most of the white solids dissolved.…”

Section: Methodsmentioning

confidence: 99%

Stereoselective Synthesis of Trisubstituted Alkenes through Sequential Iron‐Catalyzed Reductive anti‐Carbozincation of Terminal Alkynes and Base‐Metal‐Catalyzed Negishi Cross‐Coupling

Cheung

2015

Chemistry A European J

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The stereoselective synthesis of trisubstituted alkenes is challenging. Here, we show that an iron‐catalyzed anti‐selective carbozincation of terminal alkynes can be combined with a base‐metal‐catalyzed cross‐coupling to prepare trisubstituted alkenes in a one‐pot reaction and with high regio‐ and stereocontrol. Cu‐, Ni‐, and Co‐based catalytic systems are developed for the coupling of sp‐, sp2‐, and sp3‐hybridized carbon electrophiles, respectively. The method encompasses a large substrate scope, as various alkynyl, aryl, alkenyl, acyl, and alkyl halides are suitable coupling partners. Compared with conventional carbometalation reactions of alkynes, the current method avoids pre‐made organometallic reagents and has a distinct stereoselectivity.

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Section: Methodsmentioning

confidence: 99%

Stereoselective Synthesis of Trisubstituted Alkenes through Sequential Iron‐Catalyzed Reductive anti‐Carbozincation of Terminal Alkynes and Base‐Metal‐Catalyzed Negishi Cross‐Coupling

Cheung

2015

Chemistry A European J

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“…All reagents were purchased from Sigma-Aldrich, unless otherwise noted. ZnI 2 and Ni(acac) 2 were purchased from Strem Chemicals. (1S,2S)-N,N'-Dimethyl-1,2-di(naphthalene-1-yl)ethane-1,2-diamine and (1R,2R)-N,N'-dimethyl-1,2-di(naphthalene-1-yl)ethane-1,2-diamine were synthesized according to previously reported procedures.…”

Section: General Informationmentioning

confidence: 99%

“…2 A 250 mL round-bottom flask was charged with a stir bar, triphenyl phosphine (15.7 g, 60 mmol; 1.2 equiv), and imidazole (4.1 g, 60 mmol; 1.2 equiv). CH 2 Cl 2 (100 mL) was then added, and the mixture was stirred for 10 min, at which point it was homogeneous.…”

Section: Synthesis Of Electrophilesmentioning

confidence: 99%

Control of Vicinal Stereocenters through Nickel‐Catalyzed Alkyl–Alkyl Cross‐Coupling

Shibata

Makida

et al. 2017

Angewandte Chemie

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Vicinal stereocenters are found in many natural and unnatural compounds. Although metal‐catalyzed cross‐coupling reactions of unactivated alkyl electrophiles are emerging as a powerful tool in organic synthesis, there have been virtually no reports of processes that generate, much less control, vicinal stereocenters. In this investigation, we establish that a chiral nickel catalyst can mediate doubly stereoconvergent alkyl–alkyl cross‐coupling, specifically, reactions of a racemic pyrrolidine‐derived nucleophile with cyclic alkyl halides (as mixtures of stereoisomers) to produce vicinal stereocenters with very good stereoselectivity.

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“…Figure 1 shows representative cases of analytes containing nitriles and substituted alkynes, compounds 1-6. All of these analytes were successfully ionized via APPI, with compounds 1-3 ionized via direct APPI and 4-6 [28] ionized via dopantassisted APPI. In all cases, a prominent signal from the analyte ion species was detected (see Supplementary Figure S2 for the associated mass spectra).…”

Section: Detection Of [M -H] + Speciesmentioning

confidence: 99%

A Functional Group Approach for Prediction of APPI Response of Organic Synthetic Targets

Zhurov

Menin

Franco

et al. 2015

J. Am. Soc. Mass Spectrom.

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Abstract. Atmospheric pressure photoionization (APPI) is a technique of choice for ionization of non-polar molecules in mass spectrometry (MS). Reported APPI-based studies tend to focus on a selected compound class, which may contain a variety of functional groups. These studies demonstrate that APPI response frequently differs substantially, indicating a certain dependence on the functional group present. Although this dependence could be employed for APPI response prediction, its systematic use is currently absent. Here, we apply APPI MS to a judiciously-compiled set of 63 compounds containing a number of diverse functional groups commonly utilized in synthesis, reactive functional groups, as well as those containing boron and silicon. Based on the outcome of APPI MS of these compounds, we propose and evaluate a simple guideline to estimate the APPI response for a novel compound, the key properties of which have not been characterized in the gas phase. Briefly, we first identify key functional groups in the compound and gather knowledge on the known ionization energies from the smallest analogues containing said functional groups. We then consider local inductive and resonance effects on said ionization energies for the compounds of interest to estimate the APPI response. Finally, application of APPI MS to compounds of interest considered herein demonstrated extended upper mass ionization limit of 3.5 kDa for non-polymeric compounds.

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Mild and Phosphine-Free Iron-Catalyzed Cross-Coupling of Nonactivated Secondary Alkyl Halides with Alkynyl Grignard Reagents

Cited by 85 publications

References 60 publications

Stereoselective Synthesis of Trisubstituted Alkenes through Sequential Iron‐Catalyzed Reductive anti‐Carbozincation of Terminal Alkynes and Base‐Metal‐Catalyzed Negishi Cross‐Coupling

Stereoselective Synthesis of Trisubstituted Alkenes through Sequential Iron‐Catalyzed Reductive anti‐Carbozincation of Terminal Alkynes and Base‐Metal‐Catalyzed Negishi Cross‐Coupling

Control of Vicinal Stereocenters through Nickel‐Catalyzed Alkyl–Alkyl Cross‐Coupling

A Functional Group Approach for Prediction of APPI Response of Organic Synthetic Targets

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