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Takumi Yoshida, Laurean Ilies, Eiichi Nakamura
Lithium alkoxide activates a monoorganosilane to generate a transient LiH/alkoxysilane complex, which quickly reacts with aryl and alkenyl halides at 25 °C to deliver a diorganosilane product. Experimental and theoretical studies suggest that the reaction includes nucleophilic attack of LiH on the halogen atom of the organic halide to generate a transient organolithium/alkoxysilane intermediate, which undergoes quick carbon-silicon bond formation within the complex.
May 1, 2018: Organic Letters
Arzu Angı, Marius Loch, Regina Sinelnikov, Jonathan G C Veinot, Markus Becherer, Paolo Lugli, Bernhard Rieger
The influence of silicon nanocrystal (SiNC) surface characteristics obtained from different functionalization methods on the performance of LEDs was investigated. The surface of SiNCs was functionalized with hexyl chains via hydrosilylation (HS) or with organolithium reagents (OLR) and resulting SiNCs were incorporated as the emissive layer in hybrid organic/inorganic LEDs. Devices utilizing SiNCs functionalized with OLR consistently exhibited lower turn-on voltages, higher luminances and external quantum efficiencies compared to those obtained from the HS method...
April 23, 2018: Nanoscale
Nicholas Carter, Xiabing Li, Lewis Reavey, Anthony J H M Meijer, Iain Coldham
Treatment of N -Boc-2-aryl-1,2,3,4-tetrahydroquinolines with n -butyllithium in THF at -78 °C resulted in efficient lithiation at the 2-position and the organolithiums were trapped with a variety of electrophiles to give substituted products. Variable temperature NMR spectroscopy gave kinetic data that showed that the rate of tert -butoxycarbonyl (Boc) rotation was fast (Δ G ‡ ≈ 45 kJ mol-1 at -78 °C) and in situ ReactIR spectroscopy showed fast lithiation at -78 °C. By carrying out the lithiation in the presence of the chiral ligand sparteine, kinetic resolutions with very high levels of enantioselectivity were achieved...
February 7, 2018: Chemical Science
Satoshi Watanabe, Naoyuki Nakaya, Junichiro Akai, Kenji Kanaori, Toshiro Harada
A silica-supported 3-aryl H8 -BINOL-derived titanium catalyst exhibited high performance in the enantioselective arylation of aromatic aldehydes using Grignard and organolithium reagents not only under batch conditions but also under continuous-flow conditions. Even with a simple pipet reactor packed with the heterogeneous catalyst, the enantioselective production of chiral diarylmethanols could be achieved through a continuous introduction of aldehydes and mixed titanium reagents generated from the organometallic precursors...
April 18, 2018: Organic Letters
Sizhou M Liu, Dino Wu, Jeffrey W Bode
A one-step synthesis of aliphatic KATs from organocuprates is reported. Organolithium and organomagnesium reagents were readily transmetalated onto Cu(I) and coupled with a KAT-forming reagent to yield the respective aliphatic KAT. The protocol is suitable for primary, secondary and-for the first time-tertiary alkyl substrates. These protocols considerably expand the range of KATs that can be readily accessed in one step from commercially available starting materials.
April 5, 2018: Organic Letters
Barry M Trost, Chris Kalnmals
Herein, we report a valuable umpolung strategy that highlights the ambiphilic nature of the bis(phenylsulfonyl)methyl synthon and demonstrates its utility as a synthetic linchpin. While the bis(phenylsulfonyl)methyl group is typically introduced as an sp3 carbon nucleophile, we demonstrate that it can also function as an effective sp2 carbon electrophile in the presence of organolithium nucleophiles. Akyl- and aryllithiums couple with the central carbon of the bis(phenylsulfonyl)methyl unit to ultimately generate trisubstituted alkenes, comprising a formal sp3-sp2 and sp2-sp2 cross-coupling between organolithiums and bis(sulfones)...
March 15, 2018: Chemistry: a European Journal
Ulrich Wietelmann, Jan Klett
The element lithium has been discovered 200 years ago. Due to its unique properties it has emerged to play a vital role in industry, esp. for energy storage, and lithium-based products and processes support sustainable technological developments. In addition to the many uses of lithium in its inorganic forms, lithium has a rich organometallic chemistry. The development of organometallic chemistry has been hindered by synthetic problems from the start. When Wilhelm Schlenk developed the basic principles to handle and synthesize air- and moisture-sensitive compounds, the road was open to further developments...
March 1, 2018: Zeitschrift Für Anorganische und Allgemeine Chemie
Bastian Nayyar, Hazem Alnasr, Wolf Hiller, Klaus Jurkschat
The ferrocene derivative (η5 -Cp)Fe{η5 -C5 H3 -1-(ArNCH)-2-(CH2 NMe2 )} (1; Ar=2,6-iPr2 C6 H3 )) reacts diastereoselectively with LiR by carbolithiation and subsequent hydrolysis to give (η5 -Cp)Fe{η5 -C5 H3 -1-(ArHNCHR)-2-(CH2 NMe2 )} (3: R=tBu; 4: R=Ph; 5: R=Me) in high yields. For R=tBu, the organolithium derivative (η5 -Cp)Fe{η5 -C5 H3 -1-(ArLiNCHR)-2-(CH2 NMe2 )} (2) was isolated. Compound 2 reacts with GeCl2 ⋅dioxane and SnCl2 to give the metallylene amide chlorides (η5 -Cp)Fe{η5 -C5 H3 -1-(ArMNCHtBu)-2-(CH2 NMe2 )} 6 (M=GeCl) and 7 (M=SnCl), respectively, which each contain three stereogenic centers...
May 4, 2018: Angewandte Chemie
Heejin Kim, Yuya Yonekura, Jun-Ichi Yoshida
Reported is the electrophilic amination of functional organolithium intermediates with well-designed aminating reagents under mild reaction conditions using flow microreactors. The aminating reagents were optimized to achieve efficient C-N bond formation without using any catalyst. The electrophilic amination reactions of functionalized aryllithiums were successfully conducted under mild reaction conditions, within 1 minute, by using flow microreactors. The aminating reagent was also prepared by the flow method...
April 3, 2018: Angewandte Chemie
Nai-Wei Liu, Kamil Hofman, André Herbert, Georg Manolikakes
An efficient cross-coupling of sodium or lithium sulfinates with aryl iodides, using a combination of nickel and photoredox catalysis, is described. The dual catalyst system enables a versatile synthesis of aryl sulfones at room temperature in good yields and displays a broad functional group compatibility. The potential utility of this method in the late-stage diversification of complex molecules and in the conversion of organolithium reagents and sulfur dioxide into sulfones is demonstrated.
February 2, 2018: Organic Letters
Daniel W N Wilson, Alexander Hinz, Jose M Goicoechea
The synthesis and characterization of a stable phosphaethynolatoborane, [B]OCP (1, [B]=N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), is described. The increased triple bond character of the P-C bond in 1 relative to the free ion (PCO- ) is probed in a series of reactivity studies. Compound 1 readily dimerises in donor solvents to afford a cyclic five-membered 6π-aromatic compound, cyclo-P2 {C[B]}O{CO[B]} (2), which decarbonylates on UV irradiation. By contrast the nickel-mediated dimerisation of 1 affords the isomeric diphosphacyclobutene [P(CO[B])]2 ...
February 19, 2018: Angewandte Chemie
Bing Gao, Suhua Li, Peng Wu, John E Moses, K Barry Sharpless
Thionyl tetrafluoride (SOF4 ) is a valuable connective gas for sulfur fluoride exchange (SuFEx) click chemistry that enables multidimensional linkages to be created via sulfur-oxygen and sulfur-nitrogen bonds. Herein, we expand the available SuFEx chemistry of SOF4 to include organolithium nucleophiles, and demonstrate, for the first time, the controlled projection of sulfur-carbon links at the sulfur center of SOF4 -derived iminosulfur oxydifluorides (R1 -N=SOF2 ). This method provides rapid and modular access to sulfonimidoyl fluorides (R1 -N=SOFR2 ), another array of versatile SuFEx connectors with readily tunable reactivity of the S-F handle...
February 12, 2018: Angewandte Chemie
María J Rodríguez-Álvarez, Joaquín García-Álvarez, Marina Uzelac, Michael Fairley, Charles T O'Hara, Eva Hevia
Edging closer towards developing air and moisture compatible polar organometallic chemistry, the chemoselective and ultrafast addition of a range of aryllithium reagents to nitriles has been accomplished by using glycerol as a solvent, at ambient temperature in the presence of air, establishing a novel sustainable access to aromatic ketones. Addition reactions occur heterogeneously ("on glycerol conditions"), where the lack of solubility of the nitriles in glycerol and the ability of the latter to form strong intermolecular hydrogen bonds seem key to favouring nucleophilic addition over competitive hydrolysis...
February 1, 2018: Chemistry: a European Journal
Dominic Auerhammer, Merle Arrowsmith, Holger Braunschweig, Rian D Dewhurst, J Oscar C Jiménez-Halla, Thomas Kupfer
The reaction of [(cAACMe )BH3 ] (cAACMe = 1-(2,6-i Pr2 C6 H3 )-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li+ [(cAACMe H)BH2 R]- (R = sp3 -, sp2 -, or sp-hybridised organic substituent), by migration of one boron-bound hydrogen atom to the adjacent carbene carbon of the cAAC ligand. A subsequent deprotonation/salt metathesis reaction with Me3 SiCl or spontaneous LiH elimination yielded the neutral cAAC-supported mono(organo)boranes, [(cAACMe )BH2 R]...
October 1, 2017: Chemical Science
Taichi Kano, Yusuke Aota, Keiji Maruoka
A highly stereoselective synthesis of hitherto less accessible chiral α-tertiary amines with multiple structurally similar linear carbon chains was achieved through chiral auxiliary mediated addition of organolithium reagents to the geometrically well-controlled alkynyl Z-ketimines. This stereoselective nucleophilic addition offers a general approach to the asymmetric synthesis of nitrogen-containing chiral materials.
December 18, 2017: Angewandte Chemie
Mingshuo Zeng, Stephen K Murphy, Seth B Herzon
We describe the development of an enantioselective synthetic route to (+)-pleuromutilin (1), (+)-12-epi-mutilin, and related derivatives. A key hydrindanone was prepared in three steps and 48% overall yield from cyclohex-2-en-1-one. 1,4-Hydrocyanation provided a nitrile (53%, or 85% based on recovered starting material) that was converted to the eneimide 57 in 80% yield by the 1,2-addition of methyllithium to the nitrile function, cyclization, and in situ acylation with di-tert-butyldicarbonate. The eneimide 57 was employed in a 2-fold neopentylic coupling reaction with an organolithium reagent derived from the alkyl iodides (R)- or (S)-30, which contain the C11-C13 atoms of the target, to provide diastereomeric diketones in 60% or 48% yield (for coupling with (R)- or (S)-30, respectively)...
November 15, 2017: Journal of the American Chemical Society
Cristina García-Ruiz, Jack L-Y Chen, Christopher Sandford, Kathryn Feeney, Paula Lorenzo, Guillaume Berionni, Herbert Mayr, Varinder K Aggarwal
Allylboronic esters react readily with carbonyls and imines (π-electrophiles), but are unreactive toward a range of other electrophiles. By addition of an aryllithium, the corresponding allylboronate complexes display enhanced nucleophilicity, enabling addition to a range of electrophiles (tropylium, benzodithiolylium, activated pyridines, Eschenmoser's salt, Togni's reagent, Selectfluor, diisopropyl azodicarboxylate (DIAD), MeSX) in high regio- and stereocontrol. This protocol provides access to key new functionalities, including quaternary stereogenic centers bearing moieties such as fluorine and the trifluoromethyl group...
November 1, 2017: Journal of the American Chemical Society
Florian F Mulks, Shirin Faraji, Frank Rominger, Andreas Dreuw, A Stephen K Hashmi
The synthesis and characterization of (NHC)(tricyclo[,7 ]hept-1-yl)gold(I) compounds is reported. Several of these organometallic compounds could be obtained by transmetalation from the organolithium precursor to the corresponding (NHC)gold(I) chlorides. These are by far the most strained stable organogold compounds reported so far. With these new compounds we were able to efficiently and selectively accomplish the first gold-catalyzed rearrangement of organogold compounds, even better yields were obtained by the first rhodium-catalyzed rearrangement of these organogold species...
January 2, 2018: Chemistry: a European Journal
Minh H Nguyen, Kevin T O'Brien, Amos B Smith
The initial design, synthesis, and validation of polymer-supported siloxane transfer agents have been achieved that permit the direct use of organolithium reagents in the palladium-catalyzed cross-coupling reactions. Through rational design, two generations of polymer support were developed that significantly simplify product purification and the transfer agent recycling.
October 20, 2017: Journal of Organic Chemistry
Alexander P Pulis, Ana Varela, Cinzia Citti, Pradip Songara, Daniele Leonori, Varinder K Aggarwal
Nonstabilized α-O-substituted tertiary organolithium species are difficult to generate, and the α-S-substituted analogues are configurationally unstable. We now report that they can both be generated easily and trapped with a range of electrophiles with high enantioselectivity, providing ready access to a range of enantioenriched tertiary alcohols and thiols. The configurational stability of the α-S-organolithium species was enhanced by using a less coordinating solvent and short reaction times.
August 28, 2017: Angewandte Chemie
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