Effiziente Synthese von arylierten Furanen durch sequentielle Rhodium‐katalysierte Arylierung und Cycloisomerisierung von Cyclopropenen

Wang, Xiaoming; Lerchen, Andreas; Daniliuc, Constantin G.; Glorius, Frank

doi:10.1002/ange.201712019

Cited by 18 publications

(1 citation statement)

References 91 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[14] Despite the conceptual simplicity,s uccessful examples are rather rare (Scheme 1c). Them ain obstacle is the high activity but low compatibility of cyclopropenes due to ring strain, which generally makes them susceptible to ring-opening reactions in CÀHa ctivation chemistry [15] instead of cyclopropylation reactions.Thus,although various coupling reactions of arenes and cyclopropenes have been realized by the groups of Wang, Glorius,and Rovis under Rh III catalysis,the majority of such functionalizations fall under ring-scission coupling. [16,17] In 2017, by using adesigned Rh III catalyst, Rovis and co-workers reported the first redox-neutral cis-diastereoselective (2.3:1 to > 20:1 dr) synthesis of cyclopropa [c]dihydroisoquinolones (Scheme 1c), where the cyclopropene acted as aspecial olefin in this [4+ +2] annulation.…”

Section: Introductionmentioning

confidence: 99%

Rhodium(III)‐Catalyzed Enantio‐ and Diastereoselective C−H Cyclopropylation of N‐Phenoxylsulfonamides: Combined Experimental and Computational Studies

et al. 2020

View full text Add to dashboard Cite

Cyclopropane rings are aprominent structural motif in biologically active molecules.E nantio-and diastereoselective construction of cyclopropanes through C À Hactivation of arenes and coupling with readily available cyclopropenes is highly appealing but remains ac hallenge.Adual directinggroup-assisted CÀHactivation strategy was used to realizemild and redox-neutral Rh III -catalyzed CÀHa ctivation and cyclopropylation of N-phenoxylsulfonamides in ah ighly enantioselective,d iastereoselective,a nd regioselective fashion with cyclopropenyl secondary alcohols as ac yclopropylating reagent. Synthetic applications are demonstrated to highlight the potential of the developed method. Integrated experimental and computational mechanistic studies revealed that the reaction proceeds via aR h V nitrenoid intermediate,a nd Noyori-type outer sphere concerted proton-hydride transfer from the secondary alcohol to the Rh = Nb ond produces the observed trans selectivity. Figure 3. Optimized geometries,e nergy differences and ee values of the transitions tates TS3 SS and TS3 RR for the alkene insertion step in the (R)-Rh4-catalyzed cyclopropanation reaction.

show abstract

Section: Introductionmentioning

confidence: 99%

Rhodium(III)‐Catalyzed Enantio‐ and Diastereoselective C−H Cyclopropylation of N‐Phenoxylsulfonamides: Combined Experimental and Computational Studies

et al. 2020

View full text Add to dashboard Cite

show abstract

Rhodium(III)‐Catalyzed Regioselective C−H Activation/Annulation for the Diverse Pyrazole‐Core Substituted Furans

Cai

Thombal

et al. 2019

Adv Synth Catal

View full text Add to dashboard Cite

A novel and facile regioselective synthetic method for polyfunctionalized furans involving rhodium (III)-catalyzed pyrazole-or indazole-directed dual CÀ H functionalization with diazodicarbonyls has been developed. This strategy provides rapid access to diverse tetrasubstituted furans bearing various pyrazoles or indazoles. This unprecedented one-pot protocol proceeds via cascade CÀ H activation, metal-carbene formation, migratory insertion, intramolecular cyclization, and deprotonation. Ethyl 4-((1H-pyrazol-1-yl)methyl)-2-(4-methoxyphenyl)-5phenylfuran-3-carboxylate (3 j). Yellow liquid; yield -69 mg; HRMS (EI + ): m/z: calcd for C 24 H 22 N 2 O 4 : 402.1580, Found: 402.1581.Ethyl 4-((1H-pyrazol-1-yl)methyl)-2-(4-nitrophenyl)-5-phenylfuran-3-carboxylate (3 k). Yellow solid; yield -69 mg; 83%; mp 99-100°C; IR (KBr): v˜= H NMR (600 MHz, CDCl 3 ): δ = 8.27 (d, J = 9.6 Hz, 2H), 8.06 (d, J = 9.6 Hz, 2H), 7.78 (d, J = 7.2 Hz, 2H), 7.57 (d, J = 1.2 Hz, 1H),

show abstract

Single‐Electron‐Transfer‐Initiated Sequential Direct Arylation Reaction of Pyrrole with Aryl Diazonium Salts

2019

View full text Add to dashboard Cite

Direct and sequential arylations of pyrrole with a diazonium salt were initiated by single electron transfer from cobaltocene. The direct arylation reaction of pyrrole was completed within 30 min even at room temperature and the corresponding arylated product was obtained in good yield. The second arylation reaction of monoarylated heteroarenes also proceeded successfully and moderate to good yields of diarylated pyrroles were obtained. A gramscale reaction also proceeded without decreasing the yield of the product.[a] Dr.

show abstract

Effiziente Synthese von arylierten Furanen durch sequentielle Rhodium‐katalysierte Arylierung und Cycloisomerisierung von Cyclopropenen

Cited by 18 publications

References 91 publications

Rhodium(III)‐Catalyzed Enantio‐ and Diastereoselective C−H Cyclopropylation of N‐Phenoxylsulfonamides: Combined Experimental and Computational Studies

Rhodium(III)‐Catalyzed Enantio‐ and Diastereoselective C−H Cyclopropylation of N‐Phenoxylsulfonamides: Combined Experimental and Computational Studies

Rhodium(III)‐Catalyzed Regioselective C−H Activation/Annulation for the Diverse Pyrazole‐Core Substituted Furans

Single‐Electron‐Transfer‐Initiated Sequential Direct Arylation Reaction of Pyrrole with Aryl Diazonium Salts

Contact Info

Product

Resources

About