Kyoto University · Materials Science
Professor Masaharu Nakamura's research lab specializes in the development of transition-metal-catalyzed cross-coupling reactions, with a strong focus on iron-catalyzed transformations that enable chemoselective and functional-group-tolerant coupling of alkyl halides with various organometallic reagents. The lab pioneers mild, efficient, and enantioselective methods for constructing challenging carbon–carbon and carbon–heteroatom bonds, including the synthesis of optically active fluorinated ketones and all-carbon quaternary centers. Their work emphasizes sustainable catalysis, using earth-abundant iron instead of precious metals, and explores novel reactivity patterns such as carbometalation and decarboxylative allylation.
Figures are computed from collected data and may differ slightly.
An iron-catalyzed cross-coupling reaction of a primary or secondary alkyl halide with an aryl Grignard reagent proceeds under mild conditions to give the corresponding coupling product in quantitative yield.
ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTIron-Catalyzed Olefin CarbometalationMasaharu Nakamura, Atsushi Hirai, and Eiichi NakamuraView Author Information Department of Chemistry, The University of Tokyo Hongo, Bunkyo-ku, 113-0033, Japan Cite this: J. Am. Chem. Soc. 2000, 122, 5, 978–979Publication Date (Web):January 25, 2000Publication History Received26 August 1998Published online25 January 2000Published inissue 1 February 2000https://pubs.acs.org/doi/10.1021/ja983066rhttps://doi.org/
A conceptually new approach affords optically active α-fluoroketones 3 in high yields with up to 99 % ee from racemic α-fluoro-β-ketoesters 1 in the presence of a chiral phosphinooxazoline ligand 2. The palladium-catalyzed decarboxylation/allylation reaction also allows the highly enantioselective construction of an all-carbon quaternary center. dba=dibenzylideneacetone. A number of biologically active compounds bear secondary stereogenic centers next to a carbonyl group as a key structural feat
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCyclopropenone AcetalsSynthesis and ReactionsMasaharu Nakamura, Hiroyuki Isobe, and Eiichi NakamuraView Author Information Department of Chemistry, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan Cite this: Chem. Rev. 2003, 103, 4, 1295–1326Publication Date (Web):February 28, 2003Publication History Received5 June 2002Published online28 February 2003Published inissue 1 April 2003https://pubs.acs.org/doi/10.1021/cr0100244https://doi.org
Chemoselective Suzuki–Miyaura coupling of primary and secondary alkyl halides is realized by using an iron/Xantphos catalyst. Primary and secondary alkyl bromides undergo the reaction to give the coupling products in good yields. Application to the synthesis of long-chain fatty acid derivatives is also described (see scheme).
Functional-group-compatible cross-coupling reaction of alkyl halides with arylzinc reagents takes place under iron catalysis in the presence of TMEDA, producing a variety of aromatic compounds in good to excellent yield. The pronounced effect of a magnesium salt was found to be the key to the promotion of the iron-catalyzed coupling reaction.
[reaction: see text] A metalative 5-endo-dig cyclization reaction of 2-ynylphenoles or anilines effected by BuLi and ZnCl(2) produces 3-zinciobenzoheteroles in excellent yield. These intermediates have been transmetalated to the corresponding cuprates and allowed to react with electrophiles to produce a variety of 2,3-disubstituted benzofurans and indoles.
The incredible bulk: A highly C-center-selective alkynylation of nonactivated alkyl halides with the corresponding Grignard reagents is achieved by using the iron-phosphine complex 1. Primary and secondary alkyl iodides, bromides, and chlorides take part in the reaction to give the substituted alkynes in good to excellent yields. Sequential cyclization/cross-coupling reactions are also demonstrated. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Suc
Closing the ring: Thermally stable but reactive 3-zinciobenzofurans and indoles were synthesized by metalative cyclization of 2-ynyl phenols or anilines. Furthermore, a variety of extended π-conjugated molecules were obtained by Pd-catalyzed cross-coupling reactions of these heterocycles with mono- or polyhalo-substituted arenes and alkenes (R2Haln; see scheme; Bn=benzyl). Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z502920_
An active methylene compound adds to a 1-alkyne in high to quantitative yield upon heating in the presence of 0.05-5 mol % of In(OTf)3 to give an alpha-alkenylated carbonyl compound.
Sterisch abgeschirmt: Der Eisen-Phosphan-Komplex 1 vermittelt eine hoch C-selektive Alkinylierung nichtaktivierter Alkylhalogenide mit entsprechenden Grignard-Reagentien. Primäre und sekundäre Alkyliodide, -bromide und -chloride liefern in guten Ausbeuten die substituierten Alkine, die anschließend Cyclisierungen und Kreuzkupplungen eingehen können. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited
The cyclopropanation reaction of an alkene with a metal carbenoid has been studied by means of the B3LYP hybrid density functional method. The cyclopropanation of ethylene with a lithium carbenoid or a zinc carbenoid [Simmons-Smith (SS) reagent] goes through two competing pathways, methylene transfer and carbometalation. Both processes are fast for the lithium carbenoid, while, for the zinc carbenoid, only the former is fast enough to be experimentally feasible. The reaction of an SS reagent (Cl
An iron-catalyzed diboration reaction of alkynes with bis(pinacolato)diboron (B2pin2) and external borating agents (MeOB(OR)2) affords diverse symmetrical or unsymmetrical cis-1,2-diborylalkenes. The simple protocol for the diboration reaction can be extended to the iron-catalyzed carboboration of alkynes with primary and, unprecedentedly, secondary alkyl halides, affording various tetrasubstituted monoborylalkenes in a highly stereoselective manner. DFT calculations indicate that a boryliron in
A P-fused double helicene consisting of a highly distorted benzene ring, with a bending angle of 23°, has been synthesized by a tandem intramolecular phospha-Friedel-Crafts reaction. Despite the distortion and reduced aromaticity, the double helicene shows thermal and chemical stability. These are important features that make these compounds attractive for applications as a new C2-symmetric bisphosphine ligand. The simple strategy proposed in this work can be used to prepare a diverse range of d
A catalytic amount of 1,2-bis(diphenylphosphino)benzene (DPPBz) achieves selective cleavage of sp(3)-carbon-halogen bond in the iron-catalysed cross-coupling between polyfluorinated arylzinc reagents and alkyl halides, which was unachievable with a stoichiometric modifier such as TMEDA; the selective iron-catalysed fluoroaromatic coupling provides easy and practical access to polyfluorinated aromatic compounds.
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