929626-16-4Relevant articles and documents
Understanding the Activation of Air-Stable Ir(COD)(Phen)Cl Precatalyst for C-H Borylation of Aromatics and Heteroaromatics
Slack, Eric D.,Colacot, Thomas J.
supporting information, p. 1561 - 1565 (2021/02/20)
A newly developed robust catalyst [Ir(COD)(Phen)Cl] (A) was used for the C-H borylation of three dozen aromatics and heteroaromatics with excellent yield and selectivity. Activation of the catalyst was identified by the use of catalytic amounts of water, alcohols, etc., when B2pin2 was used in noncoordinating solvents, while for THF catalytic use of HBpin was required. The results were on par with the in situ based expensive system [Ir(OMe)(COD)]2/dtbbpy or Me4Phen.
NNB-type tridentate boryl ligands enabling a highly active iridium catalyst for C–H borylation
Ding, Siyi,Wang, Linghua,Miao, Zongcheng,Li, Pengfei
, (2019/04/30)
Boryl ligands play a very important role in catalysis because of their very high electron-donating property. In this paper, NNB-type boryl anions were designed as tridentate ligands to promote aryl C–H borylation. In combination with [IrCl(COD)]2/su
Highly active, separable and recyclable bipyridine iridium catalysts for C-H borylation reactions
Mamlouk, Hind,Suriboot, Jakkrit,Manyam, Praveen Kumar,Alyazidi, Ahmed,Bergbreiter, David E.,Madrahimov, Sherzod T.
, p. 124 - 127 (2018/01/17)
Iridium complexes generated from Ir(i) precursors and PIB oligomer functionalized bpy ligands efficiently catalyzed the reactions of arenes with bis(pinacolato)diboron under mild conditions to produce a variety of arylboronate compounds. The activity of this PIB bound homogeneous catalyst is similar to that of an original non-recyclable catalyst which allows it to be used under milder conditions than other reported recyclable catalysts. This oligomer-supported Ir catalyst was successfully recovered through biphasic extraction and reused for eight cycles without a loss of activity. Biphasic separation after the initial use of the catalyst led to an insignificant amount of iridium leaching from the catalyst to the product, and no iridium leaching from the catalyst was observed in the subsequent recycling runs. Arylboronate products obtained after extraction are sufficiently pure as observed by 1H and 13C-NMR spectroscopy that they do not require further purification.
Double N,B-Type Bidentate Boryl Ligands Enabling a Highly Active Iridium Catalyst for C-H Borylation
Wang, Guanghui,Xu, Liang,Li, Pengfei
supporting information, p. 8058 - 8061 (2015/07/15)
Boryl ligands hold promise in catalysis due to their very high electron-donating property. In this communication double N,B-type boryl anions were designed as bidentate ligands to promote an sp2 C-H borylation reaction. A symmetric pyridine-con
Harnessing C-H Borylation/Deborylation for Selective Deuteration, Synthesis of Boronate Esters, and Late Stage Functionalization
Kallepalli, Venkata A,Gore, Kristin A.,Shi, Feng,Sanchez, Luis,Chotana, Ghayoor A.,Miller, Susanne L.,Maleczka, Robert E.,Smith, Milton R.
, p. 8341 - 8353 (2015/09/02)
Ir-catalyzed deborylation can be used to selectively deuterate aromatic and heteroaromatic substrates. Combined with the selectivities of Ir-catalyzed C-H borylations, uniquely labeled compounds can be prepared. In addition, diborylation/deborylation reactions provide monoborylated regioisomers that complement those prepared by C-H borylation. Comparisons between Ir-catalyzed deborylations and Pd-catalyzed deborylations of diborylated indoles described by Movassaghi are made. The Ir-catalyzed process is more effective for deborylating aromatics and is generally more effective in the monodeborylation of diborylated thiophenes. These processes can be applied to complex molecules such as clopidogrel.
Regioselective conversion of arenes to N-aryl-1,2,3-triazoles Using C-H Borylation
Srinivasan, Rajavel,Coyne, Anthony G.,Abell, Chris
supporting information, p. 11680 - 11684 (2014/10/15)
A one-pot protocol for the synthesis of N-aryl 1,2,3-triazoles from arenes by an iridium-catalyzed C-H borylation/copper catalyzed azidation/click sequence is described. 1mol % of Cu(OTf)2 was found to efficiently catalyze both the azidation and the click reaction. The applicability of this method is demonstrated by the late-stage chemoselective installation of 1,2,3-triazole moiety into unactivated molecules of pharmaceutical importance.
Microwave-assisted, Ir-catalyzed aromatic C-H borylation
Zeqing, Li,Zhibin, Liang,Yuqiang, Wang,Pei, Yu
, p. 1917 - 1926 (2013/06/05)
One-step conversions of 1,3-disubstituted benzenes to aryl boronates and 2,6-disubstituted pyridines to heteroaryl boronates are described. Microwave heating was used for all reactions. [(COD)Ir(μ-OMe)]2 and 4,4′-di-tert-butyl-2,2′-bipyridine w
Sterically controlled alkylation of arenes through iridium-catalyzed C-H borylation
Robbins, Daniel W.,Hartwig, John F.
supporting information, p. 933 - 937 (2013/02/25)
Complementary chemistry: A one-pot method for the site-selective alkylation of arenes controlled by steric effects is reported. The process occurs through Ir-catalyzed C-H borylation, followed by Pd- or Ni-catalyzed coupling with alkyl electrophiles. This selectivity complements that of the typical Friedel-Crafts alkylation; meta-selective alkylation of a broad range of arenes with various electronic properties and functional groups occurs in good yield with high site selectivity. Copyright
Copper-mediated fluorination of arylboronate esters. Identification of a Copper(III) fluoride complex
Fier, Patrick S.,Luo, Jingwei,Hartwig, John F.
supporting information, p. 2552 - 2559 (2013/03/29)
A method for the direct conversion of arylboronate esters to aryl fluorides under mild conditions with readily available reagents is reported. Tandem reactions have also been developed for the fluorination of arenes and aryl bromides through arylboronate ester intermediates. Mechanistic studies suggest that this fluorination reaction occurs through facile oxidation of Cu(I) to Cu(III), followed by rate-limiting transmetalation of a bound arylboronate to Cu(III). Fast C-F reductive elimination is proposed to occur from an aryl-copper(III)-fluoride complex. Cu(III) intermediates have been generated independently and identified by NMR spectroscopy and ESI-MS.
A general strategy for the perfluoroalkylation of arenes and arylbromides by using arylboronate esters and [(phen)CuRF]
Litvinas, Nichole D.,Fier, Patrick S.,Hartwig, John F.
supporting information; experimental part, p. 536 - 539 (2012/02/16)
A versatile method for the synthesis of aryl perfluoroalkanes from arenes and aryl bromides is described. Substituted arenes or aryl bromides are converted in situ to an aryl boronate ester that readily undergoes perfluoroalkylation in air with [(phen)CuRF]. A broad range of aryl bromide substrates were perfluoroalkylated in good yield for the first time. [(phen)CuCF3] is now commercially available and has been prepared on 20g scale. Copyright
