103240-91-1Relevant articles and documents
Stereospecific allyl-aryl coupling catalyzed by in situ generated palladium nanoparticles in water under ambient conditions
Zhao, Jingming,Ye, Jiang,Zhang, Yong Jian
supporting information, p. 491 - 498 (2013/05/09)
A practical process for the stereospecific cross-coupling of secondary allylic carbonates with arylboronic acids has been developed. The reaction is catalyzed by in situ generated palladium nanoparticles (PdNPs) without any ligands and additional stabilizers in water under ambient conditions and furnishes the allyl-aryl coupling products in high isolated yields with high stereospecificities as well as excellent chemo-, regio- and E/Z-selectivities. The in situ generated PdNPs showed extraordinary catalytic activity (S/C up to 5000) even for the allyl-aryl coupling reactions of easily eliminated allylic carbonates under aqueous ambient conditions. The mechanism of the process has also been investigated.
Sulfonamidoquinoline/palladium(II)-dimer complex as a catalyst precursor for palladium-catalyzed γ-Selective and stereospecific allyl-aryl coupling reaction between allylic acetates and arylboronic acids
Makida, Yusuke,Ohmiya, Hirohisa,Sawamura, Masaya
, p. 410 - 414 (2011/10/03)
On neutral territory: A neutral palladium(II)-dimer catalyst system incorporating anionic sulfonamidoquinoline ligands is effective for the γ-selective and stereospecific allyl-aryl coupling between acyclic (E)-allylic acetates and arylboronic acids. Copy
Palladium-catalyzed γ-selective and stereospecific allyl-aryl coupling between acyclic allylic esters and arylboronic acids
Ohmiya, Hirohisa,Makida, Yusuke,Li, Dong,Tanabe, Masahito,Sawamura, Masaya
supporting information; experimental part, p. 879 - 889 (2010/03/25)
Reactions between acyclic (E)-allylic acetates and arylboronic acids in the presence of a palladium catalyst prepared from Pd(OAc)2, phenanthroline (or bipyridine), and AgSbF6 (1:1.2:1) proceeded with excellent γ-selectivity to afford allyl-aryl coupling products with E-configuration. The reactions of α-chiral allylic acetates took place with excellent α-to-γ chirality transfer with syn stereochemistry to give allylated arenes with a stereogenic center at the benzylic position. The reaction tolerated a broad range of functional groups in both the allylic acetates and the arylboronic acids. Furthermore, γ-arylation of cinnamyl alcohol derivatives afforded gem-diarylalkane derivatives containing an unconjugated alkenic substituent. The synthetic utility of this method was demonstrated by its utilization in an efficient synthesis of (+)-sertraline, an antidepressant agent. The observed γ-regioselectivity and E-1,3-syn stereochemistry were rationalized based on a Pd(II) mechanism involving transmetalation between a cationic mono(acyloxo)palladium(II) complex and arylboronic acid, and directed carbopalladation followed by syn-β-acyloxy elimination. The results of stoichiometric reactions of palladium complexes related to possible intermediates were fully consistent with the proposed mechanism.
Palladium-Catalyzed Propargylic vs. Allylic Alkylation
Keinan, Ehud,Bosch, Eric
, p. 4006 - 4016 (2007/10/02)
The relative reactivities of allylic propargylic acetates toward palladium(0)-catalyzed substitution by various nucleophiles were studied bu using three types of model substrates: (a) monofunctional allylic and propargylic acetates with similar structural properties; (b) a bifunctional substrate containing both allyl and propargyl functionalities with no apparent interaction between them; (c) conjugated bifunctional systems, in which the two functionalities may interact with one another.Palladium(0)-catalyzed substitution of propargylic acetates by various carbon nucleophiles was found to be less general than the analogous substitution of allylic acetates.Three modes of reactivity were observed, corresponding to three groups of nucleophiles; (a) stabilized carboanions such as sodium dimethyl malonate, which do not react with propargylic acetates but react readily with allylic acetates; (b) nonstabilized organometallics such as phenylzinc chloride, which react with propargylic and allylic acetates at comparable rates (reaction with the former yielding the allenic product exlusively); and (c) allyl- and allenylstannanes, which react with allylic acetates but do not react with isolated propargylic acetates (except for special cases where the propargylic acetate is also an allylic one).Certain similarities between regioselectivity phenomena in organopalladium and organocopper chemistry are discussed.
