20651-66-5Relevant articles and documents
Oxidative Addition Complexes as Precatalysts for Cross-Coupling Reactions Requiring Extremely Bulky Biarylphosphine Ligands
Ingoglia, Bryan T.,Buchwald, Stephen L.
supporting information, p. 2853 - 2856 (2017/06/07)
In this report, we describe the application of palladium-based oxidative addition complexes (OACs) as effective precatalysts for C-N, C-O, and C-F cross-coupling reactions with a variety of (hetero)arenes. These complexes offer a convenient alternative to previously developed classes of precatalysts, particularly in the case of the bulkiest biarylphosphine ligands, for which palladacycle-based precatalysts do not readily form. The precatalysts described herein are easily prepared and stable to long-term storage under air.
In-Depth Assessment of the Palladium-Catalyzed Fluorination of Five-Membered Heteroaryl Bromides
Milner, Phillip J.,Yang, Yang,Buchwald, Stephen L.
supporting information, p. 4775 - 4780 (2015/10/28)
A thorough investigation of the challenging Pd-catalyzed fluorination of five-membered heteroaryl bromides is presented. Crystallographic studies and density functional theory (DFT) calculations suggest that the challenging step of this transformation is
A Fluorinated Ligand Enables Room-Temperature and Regioselective Pd-Catalyzed Fluorination of Aryl Triflates and Bromides
Sather, Aaron C.,Lee, Hong Geun,De La Rosa, Valentina Y.,Yang, Yang,Müller, Peter,Buchwald, Stephen L.
supporting information, p. 13433 - 13438 (2015/11/09)
A new biaryl monophosphine ligand (AlPhos, L1) allows for the room-temperature Pd-catalyzed fluorination of a variety of activated (hetero)aryl triflates. Furthermore, aryl triflates and bromides that are prone to give mixtures of regioisomeric aryl fluorides with Pd-catalysis can now be converted to the desired aryl fluorides with high regioselectivity. Analysis of the solid-state structures of several Pd(II) complexes, as well as density functional theory (DFT) calculations, shed light on the origin of the enhanced reactivity observed with L1.
Studying regioisomer formation in the pd-catalyzed fluorination of aryl triflates by deuterium labeling
Milner, Phillip J.,Kinzel, Tom,Zhang, Yong,Buchwald, Stephen L.
supporting information, p. 15757 - 15766 (2015/02/02)
Isotopic labeling has been used to determine that a portion of the desired product in the Pd-catalyzed fluorination of electron-rich, non-ortho-substituted aryl triflates results from direct C-F cross-coupling. In some cases, formation of a Pd-aryne intermediate is responsible for producing undesired regioisomers. The generation of the Pd-aryne intermediate occurs primarily via ortho-deprotonation of a L·Pd(Ar)OTf (L = biaryl monophosphine) species by CsF and thus competes directly with the transmetalation step of the catalytic cycle. Deuterium labeling studies were conducted with a variety of aryl triflates.
Pd-catalyzed nucleophilic fluorination of aryl bromides
Lee, Hong Geun,Milner, Phillip J.,Buchwald, Stephen L.
supporting information, p. 3792 - 3795 (2014/04/03)
On the basis of mechanism-driven reaction design, a Pd-catalyzed nucleophilic fluorination of aryl bromides and iodides has been developed. The method exhibits a broad substrate scope, especially with respect to nitrogen-containing heteroaryl bromides, and proceeds with minimal formation of the corresponding reduction products. A facilitated ligand modification process was shown to be critical to the success of the reaction.
POLYCYCLIC RING-FUSED COMPOUND AND ORGANIC THIN FILM TRANSISTOR UTILIZING SAME
-
Page/Page column 27, (2012/11/08)
A compound for an organic thin film transistor represented by the following formula (1):
Evidence for in situ catalyst modification during the Pd-catalyzed conversion of aryl triflates to aryl fluorides
Maimone, Thomas J.,Milner, Phillip J.,Kinzel, Tom,Zhang, Yong,Takase, Michael K.,Buchwald, Stephen L.
supporting information; experimental part, p. 18106 - 18109 (2012/01/02)
A mechanistic investigation of the Pd-catalyzed conversion of aryl triflates to fluorides is presented. Studies reveal that C-F reductive elimination from a LPdII(aryl)F complex (L = t-BuBrettPhos or RockPhos) does not occur when the aryl group is electron rich. Evidence is presented that a modified phosphine, generated in situ, serves as the actual supporting ligand during catalysis with such substrates. A preliminary study of the reactivity of a LPdII(aryl)F complex based on this modified ligand is reported.
Metal-Catalyzed Carbon-Fluorine Bond Formation
-
Page/Page column 18-19, (2011/02/18)
One aspect of the invention relates to a metal-catalyzed conversion of aryl halides and sulfonates to the corresponding aryl fluorides. Another aspect of the invention relates to a metal-catalyzed conversion of heteroaryl halides and sulfonates to the corresponding heteroaryl fluorides. Another aspect of the invention relates to a metal-catalyzed conversion of vinyl halides and sulfonates to the corresponding vinyl fluorides. In certain embodiments, simple fluoride sources, such as AgF and CsF, are used. In certain embodiments, the transformations tolerate a wide range of functional groups, allowing for introduction of fluorine atoms into highly functionalized organic molecules.
Structure of ω-Arylalkyl Radicals: A 13C CIDNP Investigation
Olah, George A.,Krishnamurthy, V. V.,Singh, Brij P.,Iyer, Pradeep S.
, p. 955 - 963 (2007/10/02)
Thermolysis of a series of ω-arylalkanoyl m-chlorobenzoyl (and acetyl) peroxides at ca. 100 deg C in cyclohexanone and in hexachloroacetone was studied by using 13C chemically induced dynamic nuclear polarization.Analysis of the observed 13C polarizations indicate that all the three radicals (β-arylethyl, γ-arylpropyl and δ-arylbutyl) have open-chain structures with no evidence for aryl participation resulting in spirocycloalkylcyclohexadienyl radicals.
