Regioselective Iron‐Catalysed Cross‐Coupling Reaction of Aryl Propargylic Bromides and Aryl Grignard Reagents

Manjón‐Mata, Inés; Quirós, M. Teresa; Buñuel, Elena; Cárdenas, Diego J.

doi:10.1002/adsc.201901203

Cited by 18 publications

(4 citation statements)

References 54 publications

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“…Cárdenas, Quirós, and co-workers (2020) reported the Fe-catalyzed cross-coupling of 3-arylpropargyl bromides 127 with aryl Grignard reagents to give a mixture of 3-arylpropargylarenes 128 and 1,1-diarylallenes 129 (Scheme 57). 129 The best propargyl/allene 128/129 regioselectivity was achieved with both reagents bearing electron-donating substituents.…”

Section: Scheme 56 Fe-catalyzed Batch Coupling Of Chloroacetylene Andmentioning

confidence: 98%

Transition-Metal-Catalyzed Cross-Coupling Reactions of Grignard Reagents

Juhász¹,

Magyar²,

Hell³

2020

Synthesis

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Transition-metal-catalyzed cross-coupling of organohalides, ethers, sulfides, amines, and alcohols (and derivatives thereof) with Grignard reagents, known as the Kumada–Tamao–Corriu reaction, can be used to prepare important intermediates in the synthesis of numerous biologically active compounds. The most frequently used transition metals are nickel, palladium, and iron, but there are several examples for cross-coupling reactions catalyzed by copper, cobalt, manganese, chromium, etc. salts and complexes. The aim of this review is to summarize the most important transition-metal-catalyzed cross-coupling reactions realized in the period 2000 to 2020.1 Introduction2 Nickel Catalysis3 Palladium Catalysis4 Iron Catalysis5 Catalysis by Other Transition Metals5.1 Cobalt Catalysis5.2 Copper Catalysis5.3 Manganese Catalysis5.4 Chromium Catalysis6 Conclusion

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Section: Scheme 56 Fe-catalyzed Batch Coupling Of Chloroacetylene Andmentioning

confidence: 98%

Transition-Metal-Catalyzed Cross-Coupling Reactions of Grignard Reagents

Juhász¹,

Magyar²,

Hell³

2020

Synthesis

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“…Conversely, the Cárdenas group has demonstrated the low‐temperature coupling of alkylmagnesium halides ( 156 ) mediated by Fe(OAc) 2 and IMes ⋅ HCl, affording propargylation ( 157 ) and allenylation ( 158 ) in moderate yields (Scheme 42). [66a] Their initial mechanistic proposal also included propargyl radicals, based on the observation of homocoupling side products and on earlier alkyl‐alkyl couplings involving radical clock experiments, [66b] Subsequent work with arylmagnesium halide nucleophiles and enantiomerically enriched substrates [66c] have led the Cárdenas group to conclude that propargyl radicals are most likely not involved in the process. It is clear that a close competition between radical and non‐radical pathways is possible for iron catalyzed propargylations.…”

Section: Metal Mediated Propargylationsmentioning

confidence: 99%

Propargyl Radicals in Organic Synthesis

et al. 2021

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The appearance of propargyl radicals as synthetic intermediates has increased in recent years from a structural curiosity to a frequent occurrence. This minireview covers the synthetically relevant organic chemistry involving the intermediacy of propargyl radicals. The review is organized by the process employed in radical generation, including H-atom abstraction, propargyl-X homolyses, radical addition to enynes, reduction of polar C=X bonds, reductions of stable carbocations, and metalmediated coupling reactions. The relevant mechanisms of generation and reaction are discussed, as are applications in syntheses of target molecules of interest.

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“…[16], bromide/heteroaryl cuprate [17], and sulfonate/TMSCF 3 /Cu cat./KF [18]. The α-substitution using racemic substrates was reported as well [19][20][21][22]. Furthermore, asymmetric version using chiral ligands was developed by Fu [23][24][25] and Nishibayashi [26,27].…”

Section: Introductionmentioning

confidence: 99%

Substitution of Secondary Propargylic Phosphates Using Aryl-Lithium-Based Copper Reagents

et al. 2023

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The substitution of secondary propargylic phosphates ROP(O)(OEt)2 where R = [Ph(CH2)2]C(H)(C≡CTMS)] Ph(CH2)2CH(OP(O)(OEt)2)(C≡CTMS) with copper reagents derived from PhLi and copper salts such as CuCl, CuCN, and Cu(acac)2 was studied to establish an ArLi-based reagent system. Among the reagents prepared, PhLi/CuCl (2:1) showed 98% α regioselectivity (rs), while PhLi/Cu(acac)2 was γ selective (>99% rs). PhLi prepared in situ from PhI and PhBr by Li-halogen exchange with t-BuLi was also used for the α selective substitution. A study using the (S)-phosphate disclosed 99% enantiospecificity (es) and the inversion of the stereochemistry. The substitution of five phosphates with substituted aryl reagents produced the corresponding propargylic products with high rs and es values. Similar reactivity and selectivity were observed with 2-furyl and 2-thienyl reagents, which were prepared via direct lithiation with n-BuLi.

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Regioselective Iron‐Catalysed Cross‐Coupling Reaction of Aryl Propargylic Bromides and Aryl Grignard Reagents

Cited by 18 publications

References 54 publications

Transition-Metal-Catalyzed Cross-Coupling Reactions of Grignard Reagents

Transition-Metal-Catalyzed Cross-Coupling Reactions of Grignard Reagents

Propargyl Radicals in Organic Synthesis

Substitution of Secondary Propargylic Phosphates Using Aryl-Lithium-Based Copper Reagents

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