Copper-Catalyzed Enantioselective Allyl-Allyl Coupling between Allylic Boronates and Phosphates with a Phenol/N-Heterocyclic Carbene Chiral Ligand.

Copper-catalyzed enantioselective allyl-allyl coupling between allylboronates and either Z-acyclic or cyclic allylic phosphates using a new chiral N-heterocyclic carbene ligand, bearing a phenolic hydroxy, is reported. This reaction occurs with exceptional SN 2'-type regioselectivities and high enantioselectivities to deliver chiral 1,5-diene derivatives with a tertiary stereogenic center at the allylic/homoallylic position.

[1]  R. Shintani Recent Progress in Copper-Catalyzed Asymmetric Allylic Substitution Reactions Using Organoboron Nucleophiles , 2016, Synthesis.

[2]  Michael J. Ardolino,et al.  Branched/linear selectivity in palladium-catalyzed allyl-allyl cross-couplings: The role of ligands. , 2015, Tetrahedron.

[3]  H. Ohmiya,et al.  Copper-catalyzed enantioselective allylic cross-coupling with alkylboranes , 2015 .

[4]  A. Hoveyda,et al.  N-Heterocyclic Carbene-Copper-Catalyzed Group-, Site-, and Enantioselective Allylic Substitution with a Readily Accessible Propargyl(pinacolato)boron Reagent: Utility in Stereoselective Synthesis and Mechanistic Attributes. , 2015, Journal of the American Chemical Society.

[5]  Delong Liu,et al.  Iridium-catalyzed allyl-allyl cross-coupling of allylic carbonates with (E)-1,3-diarylpropenes. , 2015, Chemical communications.

[6]  E. Carreira,et al.  Iridium-catalyzed enantioselective allyl-allylsilane cross-coupling. , 2014, Angewandte Chemie.

[7]  H. Ohmiya,et al.  Copper-catalyzed enantioselective allylic alkylation of terminal alkyne pronucleophiles. , 2014, Journal of the American Chemical Society.

[8]  Fanke Meng,et al.  Multifunctional organoboron compounds for scalable natural product synthesis , 2014, Nature.

[9]  Michael J. Ardolino,et al.  Congested C-C bonds by Pd-catalyzed enantioselective allyl-allyl cross-coupling, a mechanism-guided solution. , 2014, Journal of the American Chemical Society.

[10]  H. Ohmiya,et al.  Copper-catalyzed enantioselective allylic substitution with alkylboranes. , 2012, Journal of the American Chemical Society.

[11]  A. Hoveyda,et al.  Copper-catalyzed enantioselective allylic substitution with readily accessible carbonyl- and acetal-containing vinylboron reagents. , 2012, Angewandte Chemie.

[12]  H. Ohmiya,et al.  Reversible 1,3-anti/syn-stereochemical courses in copper-catalyzed γ-selective allyl-alkyl coupling between chiral allylic phosphates and alkylboranes. , 2012, Journal of the American Chemical Society.

[13]  A. Hoveyda,et al.  Site- and enantioselective formation of allene-bearing tertiary or quaternary carbon stereogenic centers through NHC-Cu-catalyzed allylic substitution. , 2012, Journal of the American Chemical Society.

[14]  Michael J. Ardolino,et al.  Diastereocontrol in asymmetric allyl-allyl cross-coupling: stereocontrolled reaction of prochiral allylboronates with prochiral allyl chlorides. , 2011, Journal of the American Chemical Society.

[15]  R. Shintani,et al.  Copper-catalyzed asymmetric allylic substitution of allyl phosphates with aryl- and alkenylboronates. , 2011, Angewandte Chemie.

[16]  U. Schneider,et al.  Catalytic intermolecular allyl-allyl cross-couplings between alcohols and boronates. , 2011, Chemical communications.

[17]  J. Morken,et al.  Enantioselective construction of all-carbon quaternary centers by branch-selective Pd-catalyzed allyl-allyl cross-coupling. , 2011, Journal of the American Chemical Society.

[18]  J. Morken,et al.  Pd-catalyzed enantioselective allyl-allyl cross-coupling. , 2010, Journal of the American Chemical Society.

[19]  H. Ohmiya,et al.  Copper-catalyzed gamma-selective allyl-alkyl coupling between allylic phosphates and alkylboranes. , 2010, Journal of the American Chemical Society.

[20]  B. Feringa,et al.  Catalytic asymmetric conjugate addition and allylic alkylation with Grignard reagents. , 2008, Chemical reviews.

[21]  A. Alexakis,et al.  Enantioselective copper-catalyzed conjugate addition and allylic substitution reactions. , 2008, Chemical reviews.

[22]  E. Nakamura,et al.  Mechanism and regioselectivity of reductive elimination of pi-allylcopper (III) intermediates. , 2004, Journal of the American Chemical Society.

[23]  M. Bao,et al.  The Fate of Bis(η3 -allyl)palladium Complexes in the Presence of Aldehydes (or Imines) and Allylic Chlorides: Stille Coupling versus Allylation of Aldehydes (or Imines). , 2001, Angewandte Chemie.

[24]  J. Bäckvall,et al.  Experimental evidence supporting a CuIII intermediate in cross-coupling reactions of allylic esters with diallylcuprate species. , 2001, Chemistry.

[25]  R. Grubbs,et al.  Synthesis and activity of a new generation of ruthenium-based olefin metathesis catalysts coordinated with 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligands. , 1999, Organic letters.

[26]  J. Godschalx,et al.  Catalyzed cross-coupling of allyl bromides with allyl tin reagents , 1980 .

[27]  B. Feringa,et al.  Copper-Catalyzed Enantioselective Allyl-Allyl Cross-Coupling , 2018 .

[28]  B. Trost,et al.  Allylstannanes as electrofugal partners in allylic alkylation , 1980 .