Journal ArticleDOI
Highly Active, Air-Stable Palladium Catalysts for the C−C and C−S Bond-Forming Reactions of Vinyl and Aryl Chlorides: Use of Commercially Available [(t-Bu)2P(OH)]2PdCl2, [(t-Bu)2P(OH)PdCl2]2, and [[(t-Bu)2PO···H···OP(t-Bu)2]PdCl]2 as Catalysts
TLDR
These anionic complexes are anticipated not only to accelerate the rate-determining oxidative addition of aryl chlorides but also to stabilize the palladium complexes in the catalytic cycle.Abstract:
Air-stable palladium complexes [(t-Bu)(2)P(OH)](2)PdCl(2), [(t-Bu)(2)P(OH)PdCl(2)](2), and [[(t-Bu)(2)PO...H...OP((t-Bu)(2)]PdCl](2) serve as efficient catalysts for a variety of cross-coupling reactions of vinyl and aryl chlorides with arylboronic acids, arylzinc reagents, and thiols to yield the corresponding styrene derivatives, biaryls, and thioethers. (31)P NMR and mechanistic studies argue that the phosphinous acid ligands in the complexes can be deprotonated in the presence of a base to yield an electron-rich anionic species, which is likely a catalyst intermediate, and dimeric [[(t-Bu)(2)PO...H...OP((t-Bu)(2)]PdCl](2) was isolated and cystallographically characterized. These anionic complexes are anticipated not only to accelerate the rate-determining oxidative addition of aryl chlorides but also to stabilize the palladium complexes in the catalytic cycle.read more
Citations
More filters
Journal ArticleDOI
On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis, A Critical Review
TL;DR: A wide array of forms of palladium has been utilized as precatalysts for Heck and Suzuki coupling reactions over the last 15 years as mentioned in this paper, and there are now many suggestions in the literature that narrow the scope of types of precatalyst that may be considered true catalysts in these coupling reactions.
Journal ArticleDOI
Selected patented cross-coupling reaction technologies.
Journal ArticleDOI
Transition-Metal-Catalyzed C−S, C−Se, and C−Te Bond Formation via Cross-Coupling and Atom-Economic Addition Reactions
Journal ArticleDOI
The development of palladium catalysts for CC and Cheteroatom bond forming reactions of aryl chloride substrates
TL;DR: In this paper, the design and application of new homogeneous palladium catalysts for the formation of C C and C heteroatom bonds from aryl chloride substrates is reviewed.
Journal ArticleDOI
A General, Efficient, and Inexpensive Catalyst System for the Coupling of Aryl Iodides and Thiols
TL;DR: An efficient copper-catalyzed carbon-sulfur bond formation reaction was developed and is particularly noteworthy given its experimental simplicity, high generality, and exceptional level of functional group toleration and the low cost of the catalyst system.
References
More filters
Journal ArticleDOI
Evidence of the formation of zerovalent palladium from Pd(OAc)2 and triphenylphosphine
Journal ArticleDOI
Highly regio- and stereocontrolled synthesis of vinyl sulfides via transition-metal-catalyzed hydrothiolation of alkynes with thiols
Abstract: Regio- and stereoselectivity in the hydrothiolation of alkynes with thiols in the presence of a variety of transition-metal catalysts is investigated in detail. Among the catalysts employed, RhCl(PPh3)3 exhibits excellent catalytic ability toward the anti-Markovnikov addition of thiols (ArSH) to alkynes (RC⋮CH), which affords the corresponding vinylic sulfides (trans-RCHCHSAr) regio- and stereoselectively. The reaction may proceed by the formation of hydrorhodium sulfide species (H−[Rh]−SAr) and probably via the subsequent hydrorhodation of alkynes to provide vinylrhodium intermediates (RCHCH−[Rh]−SAr). In contrast, PdCl2(PhCN)2-catalyzed hydrothiolation of aromatic alkynes (ArC⋮CH) takes place to give the corresponding Markovnikov adducts (R(ArS)CCH2) with excellent regioselectivity, probably via thiopalladation of alkynes by palladium sulfide species (ArS−[Pd]−Cl), which may be formed by ligand-exchange reaction between PdCl2(PhCN)2 and ArSH. Furthermore, in the case of alkynes bearing propargylic proto...
Journal ArticleDOI
Air-Stable Phosphine Sulfide Ligand Precursors for Nickel-Catalyzed Cross-Coupling Reactions of Unactivated Aryl Chlorides with Aryl Grignard Reagents
George Y. Li,Will J. Marshall +1 more
TL;DR: The air-stable phosphine sulfide [(tBu)2P(S)H] serves as a ligand precursor for the efficient nickel-catalyzed cross-coupling reactions of a variety of unactivated aryl chlorides with Grignard reagents (Kumada−Tamao−Corriu reaction) as mentioned in this paper.
Journal ArticleDOI
Carbenoid or Lithium Complex of a Carbanion? Synthesis and Structure of (Me3Si)2CP(aryl)C(Cl)Li(thf)3 and LiCl Elimination To Give the Phosphirene
Journal ArticleDOI
Enantioselective Reduction of Ketones Catalyzed by Polymer-Supported Sulfonamide Using NaBH(4)/Me(3)SiCl (or BF(3) small middle dotOEt(2)) as Reducing Agent This work was supported by the Ministry of Sciences and Technology, the State Key Project of Basic Research (Project 973, No. G 2000048007).
Related Papers (5)
Palladium-catalyzed cross-coupling reactions of organoboron compounds
Norio Miyaura,Akira Suzuki +1 more