A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd‐catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example of a highly enantioselective intramolecular cyclization/cross‐coupling of olefin‐tethered aryl halides with alkyl‐, alkenyl‐ or arylboronic acids, and provides rapid access to a number of chiral compounds, such as dihydrobenzofurans, indolines, chromanes, and indanes bearing a quaternary stereocenter, in good yields with excellent enantioselectivities. The practicality of this reaction was validated in the modification of biologically complex molecules such as peptides, piperitol, CB2 receptor agonists, etc. Moreover, the synthesis of two enantiomers can be easily realized by simple change in the order of the steps in the coupling sequence.
The first example of highly enantioselective intramolecular hydroarylation of allyl aryl ethers was realized by palladium-catalyzed reductive heck reactions utilizing a new chiral sulfinamide phosphine ligand (N-Me-XuPhos). N-Me-XuPhos can be easily prepared on gram scale from readily available starting materials in a one-pot synthesis approach. A series of optically active 2,3-dihydrobenzofurans bearing a quaternary stereocenter were obtained in good yields and with excellent enantioselectivities. The practicality of this reaction was validated in the straightforward synthesis of CB2 receptor agonists. Moreover, deuterium was efficiently incorporated into the products.
A ring-opening/alkyne–carbonyl
metathesis sequence of alkyne-tethered
cyclobutanones catalyzed by AgSbF6 is realized for the
first time to furnish multisubstituted naphthyl ketones under mild
conditions. A range of substrates decorated with various substituents
at different positions were all well accommodated. Preliminary mechanistic
studies show that silver salt acted as a Lewis acid to facilitate
both C–C cleavage of the cyclobutanone moiety and the subsequent
metathesis between CO and CC bonds.
A palladium catalyzed enantioselective Heck/borylation reaction of alkene-tethered aryl iodides was realized, delivering a variety of 2,3-dihydrobenzofuranyl boronic esters in high yield with excellent enantioselectivity. Asymmetric synthesis of chromane boronic...
Ah ighly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by aP d-catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example of ah ighly enantioselective intramolecular cyclization/cross-coupling of olefin-tethered aryl halides with alkyl-, alkenyl-or arylboronic acids,and provides rapid access to an umber of chiral compounds,s uch as dihydrobenzofurans,i ndolines,c hromanes,a nd indanes bearing aquaternary stereocenter,ingood yields with excellent enantioselectivities.T he practicality of this reaction was validated in the modification of biologically complex molecules such as peptides,p iperitol, CB2 receptor agonists,e tc. Moreover,t he synthesis of two enantiomers can be easily realized by simple change in the order of the steps in the coupling sequence.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.