109613-00-5Relevant articles and documents
Solvent effect on palladium-catalyzed cross-coupling reactions and implications on the active catalytic species
Proutiere, Fabien,Schoenebeck, Franziska
, p. 8192 - 8195 (2011)
Suzuki coupling of the bifunctional substrate 1 using [Pd 2(dba)3]/PtBu3 gives selectivity for C-Cl in nonpolar solvents but for C-OTf in polar solvents. The results of computational and experimental studies suggest that the catalytically active species in polar solvents under conditions employing coordinating additives is inconsistent with monoligated [Pd(PtBu3)]. Instead, the data are consistent with an anionic palladium complex as the active species.
Synthesis of unsymmetrical biaryls by palladium-catalyzed cross coupling reactions of arenes with tetrabutylammonium triphenyldifluorosilicate, a hypervalent silicon reagent
Mowery, Molly E.,DeShong, Philip
, p. 3266 - 3270 (1999)
Palladium-catalyzed cross coupling of arenes with tetrabutylammonium triphenyldifluorosilicate, a hypervalent silicon reagent, to give unsymmetrical biaryls is reported. The Pd(0)-catalyzed process proceeds in good yield with aryl iodides, most aryl trifiates, and electron-deficient aryl bromides.
Discovery and optimisation of a selective non-steroidal glucocorticoid receptor antagonist
Brown, Angus R.,Bosies, Michael,Cameron, Helen,Clark, John,Cowley, Angela,Craighead, Mark,Elmore, Moira A.,Firth, Alistair,Goodwin, Richard,Goutcher, Susan,Grant, Emma,Grassie, Morag,Grove, Simon J.A.,Hamilton, Niall M.,Hampson, Hannah,Hillier, Alison,Ho, Koc-Kan,Kiczun, Michael,Kingsbury, Celia,Kultgen, Steven G.,Littlewood, Peter T.A.,Lusher, Scott J.,MacDonald, Susan,McIntosh, Lorraine,McIntyre, Theresa,Mistry, Ashvin,Morphy, J. Richard,Nimz, Olaf,Ohlmeyer, Michael,Pick, Jack,Rankovic, Zoran,Sherborne, Brad,Smith, Alasdair,Speake, Michael,Spinks, Gayle,Thomson, Fiona,Watson, Lynn,Weston, Mark
, p. 137 - 140 (2011)
High-throughput screening of 3.87 million compounds delivered a novel series of non-steroidal GR antagonists. Subsequent rounds of optimisation allowed progression from a non-selective ligand with a poor ADMET profile to an orally bioavailable, selective, stable, glucocorticoid receptor antagonist.
Negishi coupling reactions with [11C]CH3I: A versatile method for efficient 11C-C bond formation
Rejc, Luka,Gómez-Vallejo, Vanessa,Alcázar, Jesús,Alonso, Nerea,Andrés, José Ignacio,Arrieta, Ana,Cossío, Fernando P.,Llop, Jordi
, p. 4398 - 4401 (2018)
Herein, we present a fast, efficient and general one-pot method for the synthesis of 11C-labelled compounds via the Negishi cross-coupling reaction. Our approach, based on the in situ formation of [11C]CH3ZnI and subsequent reaction with aryl halides or triflates, has proven efficient to synthesize [11C]thymidine, a biologically relevant compound with potential applications as a proliferation marker. Theoretical calculations have shown irreversible formation of a tetracoordinated nucleophilic 11C-Zn(ii) reagent and electronic requirements for an efficient Negishi coupling.
Convenient synthesis of aromatic thiols from phenols
Arnould, Jean Claude,Didelot, Myriam,Cadilhac, Caroline,Pasquet, Marie Jeanne
, p. 4523 - 4524 (1996)
Aromatic thiols were synthesised from phenols in good yield and under mild conditions by reaction of the corresponding triflates with sodium triisopropylsilanethiolate (NaSTIPS) and subsequent deprotection.
PMHS-mediated couplings of alkynes or benzothiazoles with various electrophiles: Application to the synthesis of (-)-akolactone A
Gallagher, William P.,Maleczka Jr., Robert E.
, p. 6775 - 6779 (2003)
Polymethylhydrosiloxane (PMHS) in combination with CsF facilitates the cross-coupling of alkynes or benzothiazoles with an array of vinyl, styryl, and aryl halides or nonaflates as well as acid chlorides. Experimental and spectroscopic evidence indicates that these reactions involve the in situ generation of a siloxyl intermediate. These cross-couplings proceed relatively quickly at room temperature and under amine-free conditions. To demonstrate the applicability of the method, a total synthesis of the cyctotoxic butanolide (-)-akolactone A was carried out.
Nickel-Catalyzed Arylation/Alkenylation of tert-Cyclobutanols with Aryl/Alkenyl Triflates via a C - C Bond Cleavage
Wang, Zhen,Hu, Yuanyuan,Jin, Hongwei,Liu, Yunkui,Zhou, Bingwei
, p. 466 - 474 (2020/12/22)
Herein, we first present a nickel-catalyzed arylation and alkenylation of tert-cyclobutanols with aryl/alkenyl triflates via a C-C bond cleavage. An array of γ-substituted ketones was obtained in moderate-to-good yields, thus featuring earth-abundant nick
Dynamic Kinetic Cross-Electrophile Arylation of Benzyl Alcohols by Nickel Catalysis
Guo, Peng,Wang, Ke,Jin, Wen-Jie,Xie, Hao,Qi, Liangliang,Liu, Xue-Yuan,Shu, Xing-Zhong
supporting information, p. 513 - 523 (2021/01/12)
Catalytic transformation of alcohols via metal-catalyzed cross-coupling reactions is very important, but it typically relies on a multistep procedure. We here report a dynamic kinetic cross-coupling approach for the direct functionalization of alcohols. The feasibility of this strategy is demonstrated by a nickel-catalyzed cross-electrophile arylation reaction of benzyl alcohols with (hetero)aryl electrophiles. The reaction proceeds with a broad substrate scope of both coupling partners. The electron-rich, electron-poor, and ortho-/meta-/para-substituted (hetero)aryl electrophiles (e.g., Ar-OTf, Ar-I, Ar-Br, and inert Ar-Cl) all coupled well. Most of the functionalities, including aldehyde, ketone, amide, ester, nitrile, sulfone, furan, thiophene, benzothiophene, pyridine, quinolone, Ar-SiMe3, Ar-Bpin, and Ar-SnBu3, were tolerated. The dynamic nature of this method enables the direct arylation of benzylic alcohol in the presence of various nucleophilic groups, including nonactivated primary/secondary/tertiary alcohols, phenols, and free indoles. It thus offers a robust alternative to existing methods for the precise construction of diarylmethanes. The synthetic utility of the method was demonstrated by a concise synthesis of biologically active molecules and by its application to peptide modification and conjugation. Preliminary mechanistic studies revealed that the reaction of in situ formed benzyl oxalates with nickel, possibly via a radical process, is an initial step in the reaction with aryl electrophiles.
Ni-Catalyzed Cross-Electrophile Coupling of Aryl Triflates with Thiocarbonates via C-O/C-O Bond Cleavage
Zhu, Zhaodong,Gong, Yuxin,Tong, Weiqi,Xue, Weichao,Gong, Hegui
supporting information, p. 2158 - 2163 (2021/04/05)
A nickel-catalyzed reductive coupling of aryl triflates with thiocarbonates is reported here. Both electron-rich and -deficient aryl C(sp2)-O electrophiles as well as a class of O-tBu S-alkyl thiocarbonates are compatible with the optimized reaction conditions, as evidenced by 49 examples. The reaction also proceeds with good chemoselective cleavage of the C-O bond with regard to thioesters. This work broadens the scope of nickel-catalyzed reductive cross-electrophile coupling reactions.
Palladium-Catalyzed Synthesis of N, N-Dimethylanilines via Buchwald-Hartwig Amination of (Hetero)aryl Triflates
Pospech, Jola,Taeufer, Tobias
, p. 7097 - 7111 (2020/06/27)
This work delineates the synthesis of N,N-dimethylaniline derivatives from dimethylamines and aryl triflates. The palladium-catalyzed C-N bond formation proceeds in excellent yields, using an unsophisticated catalytic system, a mild base, and triflates as electrophiles, which are readily available from inexpensive phenols. N,N-Dimethylanilines are multifunctional reaction partners and represent useful but underutilized building blocks in organic synthesis.
