Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(20), P. 5831 - 5840
Published: Jan. 1, 2024
An Ir/Brønsted acid dual-catalyzed asymmetric cascade reaction of 2-(1-hydroxyallyl)phenols with isochroman ketals was developed, affording antifungal spiroketals high enantioselectivities.
Language: Английский
ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5796 - 5805
Published: March 25, 2025
The transition metal-catalyzed asymmetric [n + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable precursors. Herein, we report visible-light-driven, palladium-catalyzed [4 vinyl benzoxazinanones siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives satisfactory diastereo- and enantioselectivities. transient generation siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for success present cycloaddition. 13C-labeling experiments reveal pathway involving [1,3]-silyl migration process. side arm effects BOX ligand silyl steric hindrance α-ketoacylsilanes play crucial roles in stereoselectivity control, theoretical calculations provide insights into stereochemical outcome reaction.
Language: Английский
Citations
0
Organic Preparations and Procedures International, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 95
Published: April 11, 2025
Language: Английский
Citations
0
Chemical Communications, Journal Year: 2024, Volume and Issue: 60(11), P. 1448 - 1451
Published: Jan. 1, 2024
An asymmetric formal [4+2] cycloaddition of cyclic enamides with 2-(1-hydroxyallyl)phenol via iridium and Brønsted acid co-catalysis has been achieved to afford chiral N -unsubstituted spiro- , O -ketals.
Language: Английский
Citations
3
Precision Chemistry, Journal Year: 2023, Volume and Issue: 1(7), P. 423 - 428
Published: July 24, 2023
An efficient synthesis of chiral benzannulated spiroketals via catalytic asymmetric [3 + 2] cycloaddition exocyclic enol ethers with p-quinones was achieved. The transformation enabled by a N,N′-dioxides/TmIII complex as the Lewis acid catalyst and afforded series enantiomerically enriched spiroketal derivatives in good yields (up to 99%) enantioselectivities 98% ee). Topographic steric maps distribution buried volumes catalysts Cavallo's SambVca 2 tool were used elucidate enantioinduction raised ligands metal ions.
Language: Английский
Citations
9
Communications Chemistry, Journal Year: 2023, Volume and Issue: 6(1)
Published: June 19, 2023
Significant progress has been made in asymmetric synthesis through the use of transition metal catalysts combined with Lewis bases. However, a dual catalytic system involving 4-aminopyridine and received little attention. Here we show metal/Lewis base relay featuring silver acetate modified chiral pyrrolidinopyridine (PPY). It was successfully applied cycloisomerization/(2 + 3) cycloaddition reaction enynamides. Bispirocyclopentene pyrazolone products could be efficiently synthesized stereoselective economical manner (up to >19:1 dr, 99.5:0.5 er). Transformations product access stereodivergent diastereoisomers densely functionalized polycyclic derivatives. Mechanistic studies illustrated model origin uncommon chemoselectivity. In subsequent bioassays, containing privileged drug-like scaffold exhibited isoform-selective phosphodiesterase 1 (PDE1) inhibitory activity vitro. The optimal lead compound displayed good therapeutic effect for ameliorating pulmonary fibrosis via inhibiting PDE1 vivo.
Language: Английский
Citations
8
Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 508 - 513
Published: Jan. 5, 2024
The enantioselective allylic alkylation of nitro ketene aminals with racemic alcohols was realized by iridium/acid dual catalysis. An allyl group installed on the α-position in a branched-selective manner high efficiency excellent enantioselectivities (93–99% ee). protocol applied to late-stage modification neonicotinoid insecticides, which directly furnished novel analogue good insecticidal activity against Aphis craccivora (LC50 = 6.40 mg/L). On basis control experiment, an aza-ene-type reaction mechanism proposed.
Language: Английский
Citations
3
Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(13)
Published: Jan. 30, 2024
Abstract Herein, we have synthesized multifunctionalized 2‐oxa‐3‐azabicyclo[3.1.1]heptanes, which are considered potential bioisosteres for meta ‐substituted arenes, through Eu(OTf) 3 ‐catalyzed formal dipolar [4π+2σ] cycloaddition of bicyclo[1.1.0]butanes with nitrones. This methodology represents the initial instance fabricating bicyclo[3.1.1]heptanes adorned multiple heteroatoms. The protocol exhibits both mild reaction conditions and a good tolerance various functional groups. Computational density theory calculations support that mechanism likely involves nucleophilic addition nitrones to bicyclo[1.1.0]butanes, succeeded by an intramolecular cyclization. synthetic utility this novel has been demonstrated in concise synthesis analogue Rupatadine.
Language: Английский
Citations
3
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(20), P. 15743 - 15750
Published: Oct. 9, 2024
Medium-sized rings are important structural units in organic molecules of significant interest. However, their efficient synthesis, especially a highly enantioselective manner, has been formidable challenge. Herein, we report an synthesis medium-sized aza-rings by Z-retentive asymmetric allylic substitution-enabled intermolecular cascade cyclization via iridium/cinchona dual catalysis. The reaction was performed under mild conditions and with good functional group tolerance. Various nine- to eleven-membered can be afforded moderate high yields (up 98%) enantioselectivities 93% ee). utilization both Z-linear dipole precursor binary catalyst is critical for the desired reactivity.
Language: Английский
Citations
2
Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: unknown
Published: Nov. 15, 2024
An iridium-catalyzed enantioselective coupling reaction of vinyl azides and benzoxazinones provided access to a new class enantioenriched N-heterocycles, 3,4-dihydroquinolin-2(1 H )-imines.
Language: Английский
Citations
2
Organic Letters, Journal Year: 2024, Volume and Issue: 26(6), P. 1224 - 1228
Published: Feb. 2, 2024
The semipinacol rearrangement is a powerful and versatile method for constructing all-carbon quaternary stereocenters. development of catalytic asymmetric rearrangements using multifunctionalizable electrophiles remains highly sought-after in organic synthesis. In this study, enantioselective allylic cation-induced reaction was presented that enables the simultaneous construction two skipped chiral carbon centers. Chiral Ir(I)-(P,olefin) Sc(OTf)3 catalysts cooperatively initiate alkylation alkenyl cyclobutanols with alcohols, triggering ring expansion cyclobutanol moiety through stereoselective 1,2-alkyl migration. afforded range cyclopentanones bearing an α-quaternary adjacent to allyl scaffold. products were applied synthesize enantioenriched fused tricyclopentanoids four stereogenic
Language: Английский
Citations
1