The Important Role of the Byproduct Triphenylphosphine Oxide in the Magnesium(II)-Catalyzed Enantioselective Reaction of Hemiacetals and Phosphorus Ylides.

By employing a simple in situ generated magnesium catalyst, a direct asymmetric reaction between hemiacetals and phosphorus ylides was achieved through a tandem Wittig-oxa-Michael reaction sequence. Enantioenriched chromans, isochromans, and tetrahydropyrans were obtained in good chemical yields, and (-)-erythrococcamide B was synthesized in enantioenriched form. The byproduct triphenylphosphine oxide was identified as a necessary additive for this process.

[1]  Y. Fujii,et al.  Organocatalytic enantio- and diastereoselective cycloetherification via dynamic kinetic resolution of chiral cyanohydrins , 2017, Nature Communications.

[2]  W. Xiao,et al.  Enantioconvergent Copper Catalysis: In Situ Generation of the Chiral Phosphorus Ylide and Its Wittig Reactions. , 2017, Journal of the American Chemical Society.

[3]  K. Ishihara,et al.  Enantioselective Cycloaddition of Styrenes with Aldimines Catalyzed by a Chiral Magnesium Potassium Binaphthyldisulfonate Cluster as a Chiral Brønsted Acid Catalyst. , 2017, Journal of the American Chemical Society.

[4]  Ke R. Yang,et al.  Enantioselective Propargylation of Polyols and Desymmetrization of meso 1,2-Diols by Copper/Borinic Acid Dual Catalysis. , 2017, Angewandte Chemie.

[5]  E. Carreira,et al.  Enantioselective Iridium-Catalyzed Allylic Cyclizations. , 2017, Organic letters.

[6]  Lei Liu,et al.  Organocatalytic Redox Deracemization of Cyclic Benzylic Ethers Enabled by An Acetal Pool Strategy. , 2017, Angewandte Chemie.

[7]  S. Denmark,et al.  Catalytic, Enantioselective, Intramolecular Sulfenofunctionalization of Alkenes with Phenols , 2017, The Journal of organic chemistry.

[8]  Philip S. J. Kaib,et al.  Asymmetric Catalysis via Cyclic Aliphatic Oxocarbenium Ions , 2017, Synfacts.

[9]  O. Trapp,et al.  By-design enantioselective self-amplification based on non-covalent product-catalyst interactions. , 2017, Nature chemistry.

[10]  Philip S. J. Kaib,et al.  A General Catalytic Asymmetric Prins Cyclization. , 2016, Journal of the American Chemical Society.

[11]  M. White,et al.  Enantioselective Allylic C-H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis. , 2016, Angewandte Chemie.

[12]  K. Nakajima,et al.  Construction of Chiral Tri- and Tetra-Arylmethanes Bearing Quaternary Carbon Centers: Copper-Catalyzed Enantioselective Propargylation of Indoles with Propargylic Esters. , 2016, Angewandte Chemie.

[13]  Ying He,et al.  Biomimetic Approach to the Catalytic Enantioselective Synthesis of Flavonoids. , 2016, Journal of the American Chemical Society.

[14]  Walter Thiel,et al.  Nitrated Confined Imidodiphosphates Enable a Catalytic Asymmetric Oxa-Pictet-Spengler Reaction. , 2016, Journal of the American Chemical Society.

[15]  Chen Zhao,et al.  Direct Formation of Oxocarbenium Ions under Weakly Acidic Conditions: Catalytic Enantioselective Oxa-Pictet-Spengler Reactions. , 2016, Journal of the American Chemical Society.

[16]  E. Jacobsen,et al.  On- and Off-Cycle Catalyst Cooperativity in Anion-Binding Catalysis. , 2016, Journal of the American Chemical Society.

[17]  Rui Wang,et al.  Catalytic Asymmetric Ring-Opening Reactions of Aziridines with 3-Aryl-Oxindoles. , 2016, Chemistry, an Asian journal.

[18]  Rui Wang,et al.  Additive Effects on Asymmetric Catalysis. , 2016, Chemical reviews.

[19]  Jian Zhou,et al.  Activation of Chiral (Salen)AlCl Complex by Phosphorane for Highly Enantioselective Cyanosilylation of Ketones and Enones. , 2016, Journal of the American Chemical Society.

[20]  Rui Wang,et al.  Catalytic Desymmetrization of meso-Aziridines with Benzofuran-2(3H)-Ones Employing a Simple In Situ-Generated Magnesium Catalyst , 2015 .

[21]  S. Dasgupta,et al.  Enantioselective Copper(I)-Catalyzed Alkynylation of Oxocarbenium Ions to Set Diaryl Tetrasubstituted Stereocenters. , 2015, Angewandte Chemie.

[22]  X. Yao,et al.  Application of a C-C Bond-Forming Conjugate Addition Reaction in Asymmetric Dearomatization of β-Naphthols. , 2015, Angewandte Chemie.

[23]  Gavin Chit Tsui,et al.  Die organokatalytische asymmetrische Prins‐Cyclisierung , 2015 .

[24]  B. List,et al.  The organocatalytic asymmetric Prins cyclization. , 2015, Angewandte Chemie.

[25]  K. Nakajima,et al.  Copper-catalyzed enantioselective propargylic etherification of propargylic esters with alcohols. , 2015, Journal of the American Chemical Society.

[26]  Depeng Zhao,et al.  Intermolecular enantioselective dearomatization reaction of β-naphthol using meso-aziridine: a bifunctional in situ generated magnesium catalyst. , 2015, Angewandte Chemie.

[27]  Yusuke Kobayashi,et al.  A dual arylboronic acid--aminothiourea catalytic system for the asymmetric intramolecular hetero-Michael reaction of α,β-unsaturated carboxylic acids. , 2014, Organic letters.

[28]  E. Uriarte,et al.  Chromone: a valid scaffold in medicinal chemistry. , 2014, Chemical reviews.

[29]  Huiqing Yuan,et al.  Catalytic enantioselective oxidative cross-coupling of benzylic ethers with aldehydes. , 2014, Angewandte Chemie.

[30]  K. Asano,et al.  Asymmetric chroman synthesis via an intramolecular oxy-Michael addition by bifunctional organocatalysts. , 2014, Organic & biomolecular chemistry.

[31]  Yong Tang,et al.  A highly efficient and enantioselective intramolecular Cannizzaro reaction under TOX/Cu(II) catalysis. , 2013, Journal of the American Chemical Society.

[32]  Yusuke Kobayashi,et al.  A powerful hydrogen-bond-donating organocatalyst for the enantioselective intramolecular oxa-Michael reaction of α,β-unsaturated amides and esters. , 2013, Angewandte Chemie.

[33]  Depeng Zhao,et al.  Direct site-specific and highly enantioselective γ-functionalization of linear α,β-unsaturated ketones: bifunctional catalytic strategy. , 2013, Angewandte Chemie.

[34]  L. Wojtas,et al.  An asymmetric Diels-Alder reaction catalyzed by chiral phosphate magnesium complexes: highly enantioselective synthesis of chiral spirooxindoles. , 2013, Angewandte Chemie.

[35]  K. Ishihara,et al.  Chiral magnesium(II) binaphtholates as cooperative Brønsted/Lewis acid-base catalysts for the highly enantioselective addition of phosphorus nucleophiles to α,β-unsaturated esters and ketones. , 2013, Angewandte Chemie.

[36]  Zigang Li,et al.  A new strategy for efficient synthesis of medium and large ring lactones without high dilution or slow addition. , 2013, Journal of the American Chemical Society.

[37]  Lukas Hintermann,et al.  Inner workings of a cinchona alkaloid catalyzed oxa-Michael cyclization: evidence for a concerted hydrogen-bond-network mechanism. , 2013, Chemistry.

[38]  Chandra M. R. Volla,et al.  Catalytic asymmetric addition of aldehydes to oxocarbenium ions: a dual catalytic system for the synthesis of chromenes. , 2012, Organic letters.

[39]  Prantik Maity,et al.  Copper-catalyzed enantioselective additions to oxocarbenium ions: alkynylation of isochroman acetals. , 2011, Journal of the American Chemical Society.

[40]  K. Asano,et al.  Asymmetric catalytic cycloetherification mediated by bifunctional organocatalysts. , 2011, Journal of the American Chemical Society.

[41]  Shainaz M. Landge,et al.  Enantioselective Friedel-Crafts reaction of indoles with trifluoroacetaldehyde catalyzed by Cinchona alkaloids. , 2011, Chirality.

[42]  Yixiang Cheng,et al.  Organocatalytic asymmetric Michael-type/Wittig reaction of phosphorus ylides: synthesis of chiral α-methylene-δ-ketoesters. , 2011, Organic letters.

[43]  Allan M Jordan,et al.  The medicinal chemist's toolbox: an analysis of reactions used in the pursuit of drug candidates. , 2011, Journal of medicinal chemistry.

[44]  M. Matsui,et al.  Organocatalytic asymmetric direct aldol reactions of trifluoroacetaldehyde ethyl hemiacetal with aromatic methyl ketones. , 2011, The Journal of organic chemistry.

[45]  B. List,et al.  Kinetic resolution of homoaldols via catalytic asymmetric transacetalization. , 2010, Journal of the American Chemical Society.

[46]  S. Schaus,et al.  Enantioselective addition of boronates to chromene acetals catalyzed by a chiral Brønsted acid/Lewis acid system. , 2010, Angewandte Chemie.

[47]  P. Cozzi,et al.  Organocatalytic stereoselective alpha-alkylation of aldehydes with stable carbocations. , 2010, Chemistry, an Asian journal.

[48]  K. Ishihara,et al.  Magnesium(II)-binaphtholate as a practical chiral catalyst for the enantioselective direct Mannich-type reaction with malonates. , 2010, Organic letters.

[49]  Jian Zhou,et al.  Improving the atom efficiency of the Wittig reaction by a "waste as catalyst/co-catalyst" strategy. , 2010, Angewandte Chemie.

[50]  Zi-Qiang Rong,et al.  Desymmetrization of cyclohexadienones via Brønsted acid-catalyzed enantioselective oxo-Michael reaction. , 2010, Journal of the American Chemical Society.

[51]  S. Luo,et al.  Asymmetric binary-acid catalysis with chiral phosphoric acid and MgF(2): catalytic enantioselective Friedel-Crafts reactions of beta,gamma-unsaturated alpha-ketoesters. , 2010, Organic letters.

[52]  S. Matsunaga,et al.  Construction of contiguous tetrasubstituted chiral carbon stereocenters via direct catalytic asymmetric aldol reaction of alpha-isothiocyanato esters with ketones. , 2009, Journal of the American Chemical Society.

[53]  Chih-Wei Tsai,et al.  Organocatalytic enantioselective cascade Michael-Michael-Wittig reactions of phosphorus ylides: one-pot synthesis of the all-cis trisubstituted cyclohexenecarboxylates via the [1 + 2 + 3] annulation. , 2009, Organic letters.

[54]  B. Trost,et al.  Magnesium-catalyzed asymmetric direct aldol addition of ethyl diazoacetate to aromatic, aliphatic, and alpha,beta-unsaturated aldehydes. , 2009, Journal of the American Chemical Society.

[55]  T. Satyanarayana,et al.  Nichtlineare Effekte in der asymmetrischen Katalyse , 2009 .

[56]  Henri B Kagan,et al.  Nonlinear effects in asymmetric catalysis. , 2009, Angewandte Chemie.

[57]  S. Reisman,et al.  Enantioselective thiourea-catalyzed additions to oxocarbenium ions. , 2008, Journal of the American Chemical Society.

[58]  Z. Wang,et al.  BINOLate–Magnesium Catalysts for Enantioselective Hetero-Diels–Alder Reaction of Danishefsky's Diene with Aldehydes , 2008 .

[59]  Ying‐Chun Chen,et al.  Organocatalytic enantioselective Mannich-type reaction of phosphorus ylides: synthesis of chiral N-boc-beta-amino-alpha-methylene carboxylic esters. , 2008, Journal of the American Chemical Society.

[60]  T. Nakata.  Total synthesis of marine polycyclic ethers. , 2005, Chemical reviews.

[61]  M. Matsui,et al.  Practical asymmetric synthesis of beta-hydroxy-beta-trifluoromethylated ketones via the first example of the in situ generation of trifluoro-acetaldehyde and its successive asymmetric carbon-carbon bond formation reaction with chiral imines. , 2004, Chemical communications.

[62]  D. Daloze,et al.  The rational design of modified Cinchona alkaloid catalysts. Application to a new asymmetric synthesis of chiral chromanes , 2004 .

[63]  M. Braun,et al.  Titan(IV)-katalysierte dynamisch-kinetische asymmetrische Umwandlung von Alkoholen, Silylethern und Acetalen unter Kohlenstoff-Allylierung† , 2004 .

[64]  M. Braun,et al.  Titanium(IV)-catalyzed dynamic kinetic asymmetric transformation of alcohols, silyl ethers, and acetals under carbon allylation. , 2004, Angewandte Chemie.

[65]  M. Faul,et al.  Strategy and methodology development for the total synthesis of polyether ionophore antibiotics. , 2000, Chemical reviews.

[66]  H. Gröger,et al.  Zur Perfektionierung der asymmetrischen Katalyse: Additive und Co-Katalysatoren , 1999 .

[67]  H. Gröger,et al.  Towards Perfect Asymmetric Catalysis: Additives and Cocatalysts. , 1999, Angewandte Chemie.

[68]  Davidr . Evans,et al.  Chiral Magnesium Bis(sulfonamide) Complexes as Catalysts for the Merged Enolization and Enantioselective Amination of N-Acyloxazolidinones. A Catalytic Approach to the Synthesis of Arylglycines , 1997 .

[69]  Carsten Bolm,et al.  Asymmetrische Autokatalyse mit Chiralitätsverstärkung , 1996 .

[70]  C. Bolm,et al.  Asymmetric Autocatalysis with Amplification of Chirality , 1996 .