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The addition of a B-H bond to an unsaturated bond (polarized or unpolarized) is a powerful and atom-economic tool for the synthesis of organoboranes. In recent years, s-block organometallics have appeared as alternative catalysts to transition-metal complexes, which traditionally catalyze the hydroboration of unsaturated bonds. Because of the recent and rapid development in the field of hydroboration of unsaturated bonds catalyzed by alkali (Li, Na, K) and alkaline earth (Mg, Ca, Sr, Ba) metals, we provide a detailed and updated comprehensive review that covers the synthesis, reactivity, and application of s-block metal catalysts in the hydroboration of polarized as well as unsaturated carbon-carbon bonds. Moreover, we describe the main reaction mechanisms, providing valuable insight into the reactivity of the s-block metal catalysts. Finally, we compare these s-block metal complexes with other redox-neutral catalytic systems based on p-block metals including aluminum complexes and f-block metal complexes of lanthanides and early actinides. In this review, we aim to provide a comprehensive, authoritative, and critical assessment of the state of the art within this highly interesting research area.
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(Hetero)arylsulfur compounds where the S atom is in the oxidation state VI represent a large percentage of the molecular functionalities present in organic chemistry. More specifically, (hetero)aryl-SVI fluorides have recently received enormous attention because of their potential as chemical biology probes, as a result of their reactivity in a simple, modular, and efficient manner. Whereas the synthesis and application of the levelâ 1 fluorination at SVI atoms (sulfonyl and sulfonimidoyl fluorides) have been widely studied and reviewed, the synthetic strategies towards higher levels of fluorination (levelsâ 2 to 5) are somewhat more limited. This Minireview evaluates and summarizes the progress in the synthesis of highly fluorinated aryl-SVI compounds at all levels, discussing synthetic strategies, reactivity, the advantages and disadvantages of the synthetic procedures, the proposed mechanisms, and the potential upcoming opportunities.
Assuntos
Fluoretos , Halogenação , Fluoretos/química , OxirreduçãoRESUMO
A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that the organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within the catalytic cycle without modifying the oxidation state. All steps have been validated, including the catalytic insertion of SO2 into Bi-C bonds, leading to a structurally unique O-bound bismuth sulfinate complex. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.
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A family of aryl dinuclear bismuthane complexes has been successfully synthesized and characterized. The two bismuth centers are bonded to various xanthene-type backbones, which differ in ring-size and flexibility, resulting in complexes with different intramolecular BiBi distances. Moreover, their pentavalent Bi(v) analogues have also been prepared and structurally characterized. Finally, the synergy between bismuth centers in catalysis has been studied by applying dinuclear bismuthanes 5-8 to the catalytic oxidative cleavage of 1,2-diols. Unfortunately, no synergistic effects were observed and the catalytic activities of dinuclear bismuthanes and triphenylbismuth are comparable.
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Correction for 'Dibismuthanes in catalysis: from synthesis and characterization to redox behavior towards oxidative cleavage of 1,2-diols' by Marc Magre et al., Org. Biomol. Chem., 2021, DOI: 10.1039/d1ob00367d.
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A magnesium-catalyzed regiodivergent C-O bond cleavage protocol is presented. Readily available magnesium catalysts achieve the selective hydroboration of a wide range of epoxides and oxetanes yielding secondary and tertiary alcohols in excellent yields and regioselectivities. Experimental mechanistic investigations and DFT calculations provide insight into the unexpected regiodivergence and explain the different mechanisms of the C-O bond activation and product formation.
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A magnesium-catalyzed hydroboration of alkynes providing good yields and selectivities for a wide range of terminal and symmetrical and unsymmetrical internal alkynes has been developed. The compatibility with many functional groups makes this magnesium catalyzed procedure attractive for late stage functionalization. Experimental mechanistic investigations and DFT calculations reveal insights into the reaction mechanism of the magnesium catalyzed protocol.
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Asymmetric catalysis with readily available, cheap, and non-toxic alkaline earth metal catalysts represents a sustainable alternative to conventional synthesis methodologies. In this context, we describe the development of a first MgII -catalyzed enantioselective hydroboration providing the products with excellent yields and enantioselectivities. NMR spectroscopy studies and DFT calculations provide insights into the reaction mechanism and the origin of the enantioselectivity which can be explained by a metal-ligand cooperative catalysis pathway involving a non-innocent ligand.
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Simple enantioselective synthesis of 6,6-disubstituted pentafulvenes bearing chiral pendant hydroxy groups are attained by cascade reactivity using commercially available proline-based organocatalysts. Condensation of cyclopentadiene with the acetyl function of a 1,2-formylacetophenone, followed by cyclization of a resulting fulvene-stabilized carbanion with the formyl group, generates bicyclic chiral alcohols with initial er values up to 94:6. Exceptional enantio-enrichment of the resultant alcohols results upon crystallization-even near racemic samples spontaneously de-racemize. This enables new families of substituted cyclopentadienes that are both enantiomerically and diastereomerically pure to be rapidly attained.
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Asymmetric hydrogenation is one of the most efficient and atom-economical tools to prepare chiral molecules. However, the enantiodiscrimination of simple, minimally functionalized olefins is still challenging and requires more sophisticated ligand design. Herein, we discuss our progress in the successful development of ligand design for the iridium-catalyzed asymmetric hydrogenation of minimally functionalized olefins.
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A series of cationic fluorotriarylbismuthonium salts bearing differently substituted aryl groups (Ar = 9,9-Me2-9H-xanthene, Ph, Mes, and 3,5-tBu-C6H3) have been synthesized and characterized. While the presence of simple phenyl substituents around the Bi center results in a polymeric structure with three Bi centers in the repeating monomer, substituents at the ortho- and meta-positions lead to cationic mono- and dinuclear fluorobismuthonium complexes, respectively. Preparation of all compounds is accomplished by fluoride abstraction from the parent triaryl Bi(V) difluorides using NaBArF (BArF - = B[C6H3-3,5-(CF3)2]4 -). Structural parameters were obtained via single crystal X-ray diffraction (XRD), and their behavior in solution was studied by NMR spectroscopy. Trinuclear and binuclear complexes are held together through one bridging fluoride (µ-F) between two Bi(V) centers. In contrast, the presence of Me groups in both ortho-positions of the aryl ring provides the adequate steric encumbrance to isolate a unique mononuclear nonstabilized fluorotriarylbismuthonium cation. This compound features a distorted tetrahedral geometry and is remarkably stable at room temperature both in solution (toluene, benzene and THF) and in the solid state.
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A new reduction of carbamates to N-methyl amines is presented. The magnesium-catalyzed reduction reaction allows the conversion of cyclic and linear carbamates, including N-Boc protected amines, into the corresponding N-methyl amines and amino alcohols which are of significant interest due to their presence in many biologically active molecules. Furthermore, the reduction can be extended to the formation of N-trideuteromethyl labeled amines.
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A regio- and stereoselective magnesium-catalyzed hydrostannylation of internal and terminal alkynes has been developed. Excellent yields and selectivities are obtained for a wide range of terminal and internal symmetrical and unsymmetrical alkynes by using this alkaline earth metal catalyst as an effective alternative to transition metal catalysts.
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The chemoselective reduction of α,ß-unsaturated ketones by use of an economic and readily available Mg catalyst has been developed. Excellent yields for a wide range of ketones have been achieved under mild reaction conditions, short times, and low catalyst loadings (0.2-0.5 mol %).
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A simple and efficient catalytic system for a chemo- and regioselective ortho-alkenylation of anilines is presented. The new magnesium-catalyzed reaction allows the use of a wide range of alkynes and anilines with different electronic and steric properties and provides free as well as protected anilines with excellent yields.
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Stabilized AlHCl(2)·(THF)(2) hydroaluminates RC≡CH with exceptional chemo-, regio- and stereoselectivity under efficient ZrCl(2)(η-C(5)Me(5))(2) catalysis (2-5 mol%). The resulting vinyl alanes undergo palladium cross-coupling with a wide range of sp(2) electrophiles (aryl, heteroaryl and vinyl halides/pseudohalides) in good to excellent yields.