Abstract: Besides numerous synthetic and biological applications, the catalytic construction of chiral Swaminathan ketones and their analogues possessing a bicyclo[5.4.0]undecane core structure has remained challenging for the scientific community for over four decades. Not more than five Swaminathan ketones (S. ketones) and their analogues are known in the literature to date. Herein, we report an unprecedented organocatalytic asymmetric desymmetrization strategy for the synthesis of chiral S. ketones and their analogues with excellent enantioselectivities from the corresponding 2-alkyl-2-(3-oxobutyl)-cycloheptane-1,3-diones via amine/acid-catalysed conformation-controlled intramolecular aldol condensation.
Abstract: Structurally complexcedrane scaffolds were synthesized in very good yields with high chemo-and diastereoselectivities in a sequential one-pot manner. A combination of intermolecular olefination, intramolecular Michael and Michael reactions or intermolecular olefination, intramolecular Michael and aldol reactions were used as the key steps from the readily available hydroxy-p-quinonebutanals and phosphoranes with catalytic amounts of quinine at ambient temperatures for a few hours.This is a unique one-pot combination of coupling and annulation routes for the green synthesis of a library of tricyclicpseudo-terpenoids(cedranescaffolds) with high selectivity and yields. Organocatalytic ring isomerization was highlighted through transforming one ring into another one by retro-cyclization. We have discussed thoroughly mechanistic aspects of these tandemcoupling/annulation and ring isomerization reactions based on control experiments and X-ray crystal structure analssis.
by suing simple substarates abd conditions.
Abstract: Lawsone aldehydes were directly transformed into the biologically important, unique carbon skeleton of chiral methanobenzo[f]azulenes/methanodibenzo[a,d][7]annulenes in high dr and ee and in very good yields by using quinine-thiourea-catalyzed tandem Wittig/intramolecular Michael/intramolecular aldol reactions. This asymmetric catalytic tandem protocol will be highly useful because these final molecules are basic skeletons of important antibiotics.
by suing simple substarates abd conditions.
Abstract: An ideal stereo selective insertion of in situ generated benzynesion to laws ones through dominofomal[2++2]- cyckiaddition followed by rearrangementis disclosed. The reaction allowed for the preparation of biologically important benzannulated bicyclo[3.3.0] octanes good yield sand with excellent selectivities
by suing simple substarates abd conditions.
Abstract: Powerful asymmetric desymmetrization of thiane-3,5-diones through formal [3+3] cycloaddition with alkyl vinyl ketones has been disclosed to access functionally rich 2-thiabicyclo[3.3.1]nonanes in very good yields with excellent enantio- and diastereoselectivities by using organocatalysis.
Abstract:Asymmetric synthesis of drug-like functionalized spiro[chroman-3,3′-indolin]-2′-ones 5 containing three contiguous stereocenters with high diastereo- and enantioselectivities was achieved using the reflexive-Michael (r-M) reaction of unmodified hydroxyenals 1 with various (E)-3-alkylideneindolin-2-ones 2 in the presence of (R)-DPPOTMS/AcOH (R)-3/4b as a catalyst at room temperature. Chiral spiro[chroman-3,3′-indolin]-2′-ones 5 were transformed into the functionalized spiranes 7, 9, and 10 in good yields with high selectivity through Wittig, TCRA, acetal protection and reduction reactions, respectively. Supporting evidence for the reaction pathway through the formation of the important catalytic species of aminals was observed through NMR and ESI-HRMS analysis of an ongoing reaction between 1 and (R)-3 in CDCl3 and also shown by the structural requirement in hydroxyenals 1 to generate the aminals with (R)-3 through controlled experiments.
Abstract:Creating sequential one-pot combinations of multi-component reactions (MCRs) and multi-catalysis cascade (MCC) reactions is a challenging task that has already emerged as a new technology in synthetic organic chemistry. Through one-pot sequential combination of MCRs/MCC reactions, the chemical products (fine chemicals, agrochemicals and pharmaceuticals) that add value to our lives can be produced with less waste and greater economic benefits. Within this emerging area, we describe our recent developments and designs for sequential one-pot MCRs/MCC reactions to facilitate their realization as biomimetics in organic chemistry.
Abstract:The cover picture shows a perspective of organo-click chemistry depicting the bringing together of simple reagents, and amino acid and copper/copper sulfate catalysts to produce spirotriones, which are antioxidant compounds. Unlike conventional methods, organo-click chemistry produces stereospecific products with very good yields in a single operation. Multicomponent reactions catalyzed by amino acids and copper sulfate together with simple reagents depicted here support the potential of a rich variety of chemistries available to the prebiotic world and beyond. For more information see the article by D. B. Ramachary and C. F. Barbas III on p. 5323 ff. The picture was designed by Michael Pique at the Scripps Research Institute.
Abstract: Biologically important, less-explored natural products of sexually deceptive chiloglottones, antimicrobial dialkylresorcinols, and their many analogues were synthesized in very good yields in a sequential two-pot manner by using an organocatalytic reductive coupling reaction as the key step. Highlighted on Journal Cover Page