105735-62-4Relevant articles and documents
Lithiation reactions catalyzed by linear and cross-linked arene-based polymers. Generation of functionalized organolithium compounds
Candela,Gomez,Yus
, p. 795 - 801 (2004)
Lithiation of various substrates, such as chlorinated acetals, α-chloro ether, dichloro derivatives benzo-fused heterocycles, and allyl and benzyl derivatives, with excess lithium powder in the presence of a catalytic amount of soluble linear or insoluble cross-linked arene (naphthalene or biphenyl)-based polymers yields the expected organolithium intermediates. The latter react with electrophiles either in two steps or under Barbier-type reaction conditions to afford the corresponding adducts. The catalyst is easily recuperated by filtration at the end of the process, and the procedure can be regarded as a reasonable alternative to the use of free arenes as electron carrier in lithiation reactions.
Pd-Catalyzed Conjunctive Cross-Coupling between Grignard-Derived Boron “Ate” Complexes and C(sp2) Halides or Triflates: NaOTf as a Grignard Activator and Halide Scavenger
Lovinger, Gabriel J.,Aparece, Mark D.,Morken, James P.
supporting information, p. 3153 - 3160 (2017/03/11)
Catalytic enantioselective conjunctive cross-couplings that employ Grignard reagents are shown to furnish an array of nonracemic chiral organoboronic esters in an efficient and highly selective fashion. The utility of sodium triflate in facilitating this reaction is two-fold: it enables “ate” complex formation and overcomes catalytic inhibition by halide ions.
Synthesis and application of benzyl-TMS derivatives as bench stable benzyl anion equivalents
Das, Manas,O'Shea, Donal F.
, p. 6448 - 6460 (2013/07/26)
The regioselective benzylic metalation of toluenes using BuLi/KO tBu/TMP(H) (LiNK metalation conditions) and subsequent transmetalation to Si by reaction with TMSCl provides a general one-pot procedure for the synthesis of substituted benzyltrimethylsilanes. ArCH 2Si(Me)3 derivatives are bench stable reagents yet can serve as benzyl anion equivalents under mild reaction conditions. Following activation with fluoride they can successfully participate in a wide range of additions to both non-enolizable and enolizable carbonyls. In addition, their use in the synthesis of isochromanones and trifluoromethylated amines is illustrated. The broad synthetic scope and mild practical conditions of use for ArCH2Si(Me)3 reagents demonstrate their general potential as benzyl anion equivalents.
Multifaceted palladium catalysts towards the tandem diboration-arylation reactions of alkenes
Penno, Dirk,Lillo, Vanesa,Koshevoy, Igor O.,Sanau, Mercedes,Ubeda, M. Angeles,Lahuerta, Pascual,Fernandez, Elena
supporting information; experimental part, p. 10648 - 10655 (2009/12/01)
Novel Pd26+ compounds have been synthesized in high yield. These compounds and their Pd24+ counterparts as synthetic precursors mediate the diboration of vinylarenes and aliphatic 1-alkenes, and under mild and basic reaction conditions they produce a variety of 1,2-diboronate esters with excellent conversions and chemo-selectivities. The presence of bis(catecholato)diboron (B2cat2) favours the reduction of PdIII to PdII, while the catalytic precursor of PdII is transformedinto Pd0-nanoparticles. An "in situ" catalytic tandem reaction has been designed to transform the diboronate intermediates into the monoarylated product, which after oxidative workup, provides the carbohydroxylated adduct. Eventually, the same catalyst performs both sequences with total conversion from the alkene.
