Asymmetric 2,4-Dienylation/[4 + 2] Annulation Cascade to Construct Fused Frameworks via Auto-Tandem Palladium Catalysis.

A palladium catalyzed tandem reaction between ortho-functionalized aryl enones and 2,4-dienyl carbonates has been presented, proceeding through sequential 2,4-dienylation/Michael addition/π-σ-π isomerization/allylic alkylation. A broad array of enantioenriched architectures having fused and spirocyclic frameworks are constructed in moderate to excellent yields and stereoselectivity. Notably, the intrinsic intramolecular Diels-Alder reaction pattern of the dienylated intermediates is well reversed via Pd(0)-π-Lewis base catalysis.

[1]  X. Cao,et al.  Palladium-Catalyzed Asymmetric Cascade Intramolecular Cyclization/Intermolecular Michael Addition Reaction of Allenyl Benzoxazinones with 1-Azadienes. , 2022, Organic letters.

[2]  Ying‐Chun Chen,et al.  Use of (E,E)-Dienoic Acids as Switchable (E,E)- and (Z,E)-Dienyl Anion Surrogates via Ligand-Controlled Palladium Catalysis. , 2022, Journal of the American Chemical Society.

[3]  Ying‐Chun Chen,et al.  Asymmetric Auto-Tandem Palladium Catalysis for 2,4-Dienyl Carbonates: Ligand-Controlled Divergent Synthesis. , 2022, Angewandte Chemie.

[4]  Z. Zuo,et al.  Enantioselective access to tricyclic tetrahydropyran derivatives by a remote hydrogen bonding mediated intramolecular IEDHDA reaction , 2021, Nature Communications.

[5]  M. Yus,et al.  Diels-Alder reactions of 1-amino-1,3-dienes and related systems , 2021, Tetrahedron.

[6]  Ying‐Chun Chen,et al.  A Palladium Complex as an Asymmetric π-Lewis Base Catalyst for Activating 1,3-Dienes. , 2021, Journal of the American Chemical Society.

[7]  Anilesh Kumar,et al.  Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control. , 2021, Chemical reviews.

[8]  F. Zubkov,et al.  IntraMolecular Diels–Alder Reactions of Vinylarenes and Alkynyl Arenes (the IMDAV Reaction) , 2021, Synthesis.

[9]  Herbert Waldmann,et al.  Ligand-Directed Divergent Synthesis of Carbo- and Heterocyclic Ring Systems. , 2018, Angewandte Chemie.

[10]  C. Maichle‐Mössmer,et al.  Intramolecular Diels-Alder Reactions of Tethered Enoate Substituted Furans Induced by Dialkylaluminum Chloride. , 2017, The Journal of organic chemistry.

[11]  B. List,et al.  Catalytic Asymmetric Intramolecular [4+2] Cycloaddition of In Situ Generated ortho-Quinone Methides. , 2017, Angewandte Chemie.

[12]  Hong Huang.  The Diels-Alder Reaction and its Applications in the Total Synthesis of Natural Products , 2016 .

[13]  L. Bouchez,et al.  Diels-Alder Cycloaddition in Medicinal Chemistry , 2016 .

[14]  S. Danishefsky,et al.  Intramolecular Diels-Alder reactions of cycloalkenones: translation of high endo selectivity to trans junctions. , 2012, Journal of the American Chemical Society.

[15]  Ying‐Chun Chen,et al.  Aminocatalytic asymmetric Diels-Alder reactions via HOMO activation. , 2012, Accounts of chemical research.

[16]  Shaomin Ji,et al.  Thiophene‐Inserted Aryl–Dicyanovinyl Compounds: The Second Generation of Fluorescent Molecular Rotors with Significantly Redshifted Emission and Large Stokes Shift , 2011 .

[17]  T. Molinski,et al.  Assembly of the isoindolinone core of muironolide A by asymmetric intramolecular Diels-Alder cycloaddition. , 2011, Organic letters.

[18]  G. Bernardinelli,et al.  Chiral ruthenium Lewis acid catalyzed intramolecular Diels-Alder reactions. , 2010, Organic letters.

[19]  R. Munakata,et al.  Recent advances in natural product synthesis by using intramolecular Diels-Alder reactions. , 2005, Chemical reviews.

[20]  D. MacMillan,et al.  Enantioselective organocatalytic intramolecular Diels-Alder reactions. The asymmetric synthesis of solanapyrone D. , 2005, Journal of the American Chemical Society.

[21]  Davidr . Evans,et al.  Chiral C2-Symmetric Cu(II) Complexes as Catalysts for Enantioselective Intramolecular Diels−Alder Reactions. Asymmetric Synthesis of (−)-Isopulo'upone , 1997 .

[22]  K. Ishihara,et al.  A New Powerful and Practical BLA Catalyst for Highly Enantioselective Diels−Alder Reaction: An Extreme Acceleration of Reaction Rate by Brønsted Acid , 1996 .

[23]  Raquel P. Herrera,et al.  Enantioselective OrganocatalyticDiels-Alder Reactions , 2010 .

[24]  D. Craig.  Stereochemical aspects of the intramolecular Diels–Alder reaction , 1987 .