Extrapolation of the gold-catalyzed cycloisomerization to the palladium-catalyzed cross-coupling/cycloisomerization of acetylenic alcohols for the synthesis of polysubstituted furans:Scope and application to tandem processes

This paper describes the development of an integrated approach for the preparation of diverse furan derivatives from acetylenic alcohols by gold and palladium catalyzed π-activation chemistry.Notably,this new method was found to be amenable to cyclooctyl-containing substrates,which represents a significant extension to this methodology compared with our previous reports.Furthermore,this newly developed method allowed for the direct construction of cyclooctyl furans from their synthetic precursors under Sonogashira conditions.Experimental results revealed that palladium played two major functions in these reactions,including（1） an essential catalyst in the cross-coupling reaction of the substrates;and（2）facilitating the cyclization of the acetylenic alcohol intermediates through a typical π-activation process.The scope of this chemistry was highlighted by the one-pot synthesis of 3-iodofuran,which provided an opportunity for further functionalization（via coupling methods）.Finally,the AuBr3 protocol was also elaborated to domino cyclization/C-H activation reactions,as well as the cyclization of acyclic precursors.Taken together,the results of this study demonstrate that gold and palladium catalysts can be used to complement each other in cyclization reactions.

NHC-Boryl Radical Catalysis for Cycloisomerization With C–C Triple Bond Reorganization

Our present study unveils a new and efficient N-heterocyclic carbene(NHC)-boryl radical-catalyzed cycloisomerization of N-(2-ethynylaryl)arylamides.This catalytic process is triggered by the addition of an NHC-boryl radical to the alkynyl moiety,followed by a radical cascade comprising of an intramolecular cyclization,successive 1,5-and 1,2-aryl migrations,and the reorganization of a C–C triple bond.

Synergy of activating substrate and introducing C–H…O interaction to achieve Rh2(II)-catalyzed asymmetric cycloisomerization of 1,n-enynes

We report the first Rh2(II)-catalyzed asymmetric cycloisomerization of activated enynes to provide cyclopropane-fused tetrahydropyridines in good yields and excellent enantioselectivities under mild conditions.The activated group,CHZ(Z is electronwithdrawing group(EWG)),in the enyne substrates exerts two synergetic roles,one is to activate alkyne for the cyclopropanation reaction;the other is to introduce the C–H…O interaction between substrate and catalyst(reducing the energy barrier of the reaction).This double-mode activation was supported by both density functional theory(DFT)calculations and experimental tests.This strategy was also extended to other CH2 Z(Z can be OH,OMe,F)as activating groups that made the CH2 more acidic so that the substrates could also form increased C–H…O interaction with the catalyst.

Total synthesis of a putative yuzurimine-type Daphniphyllum alkaloid C_(14)–epi-deoxycalyciphylline H

One of the largest subfamilies within the famous Daphniphyllum alkaloid family is made up of the yuzurimine-type(or macrodaphniphyllamine-type) alkaloids. Their complex aza-polycyclic caged structures, several contiguous stereogenic centers, and vicinal all-carbon quaternary centers make these alkaloids formidable challenge for synthetic chemists. Recently, synthesis of these alkaloids has received extensive attention from our community. Herein, we wish to report the total synthesis of C_(14)–epideoxycalyciphylline H, a putative member of yuzurimine-type alkaloid subfamily. Key transformations employed in our approach include an intramolecular Prins reaction and a Pd-catalyzed enyne cycloisomerization. In addition, synthesis of a daphnezomine L-type alkaloid, paxdaphnidine A, was also studied.

Pd3 cluster catalysis: Compelling evidence from in operando spectroscopic, kinetic, and density functional theory studies

Identification of metal cluster catalysis is a topic that is being investigated since a long time. Here, we report a Pd3 metal cluster catalytic reaction investigated by means of operando studies. We discovered that atomically defined tri-nuclear palladium (Pd3) is a surprisingly active catalyst for the cycloisomerization of 2-phenylethynylaniline. Operando1H NMR spectroscopy and X-ray extended absorption fine structure (EXAFS) measurements have indicated that the structural integrity of such a catalyst remains intact throughout the reaction, which has also been confirmed by an ex situ X-ray photoelectron spectroscopy (XPS) study and catalyst recycling experiments. Kinetic data derived from operando IR spectroscopy measurements have shown that Pd3is the active catalytic species. Density functional theory calculations have revealed a reaction pathway consistent with the kinetic data, further supported by NMR titration and X-ray crystal structure studies. Overall, the present study presents a clear example of metal cluster catalysis. [Figure not available: see fulltext.] © 2016, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.