anti-Diastereo- and enantioselective carbonyl (hydroxymethyl)allylation from the alcohol or aldehyde oxidation level: allyl carbonates as allylmetal surrogates.

Enantioselective transfer hydrogenation of carbonate 1a in the presence of aromatic, allylic, or aliphatic alcohols 2a-2i employing a cyclometalated iridium C,O-benzoate derived from allyl acetate, 4-cyano-3-nitrobenzoic acid and (S)-SEGPHOS delivers products of (hydroxymethyl)allylation 4a-4i in good isolated yields (60-74%), good anti-diastereoselectivities (5:1-10:1 dr) and exceptional levels of enantiocontrol (93-99% ee). Under identical reaction conditions, but in the presence of isopropanol, aldehydes 3a-3i are converted to an equivalent set of adducts 4a-4i in good isolated yields (58-74%), good anti-diastereoselectivities (4:1-14:1 dr), and exceptional levels of enantiocontrol (95-99% ee). Thus, identical sets of adducts 4a-4i are produced with equal facility from the alcohol or aldehyde oxidation level. These studies represent the first general method for enantioselective carbonyl (hydroxymethyl)allylation, a process that has no highly stereoselective counterpart in conventional allylmetal chemistry.

[1]  M. Krische,et al.  Diastereo- and enantioselective anti-alkoxyallylation employing allylic gem-dicarboxylates as allyl donors via iridium-catalyzed transfer hydrogenation. , 2010, Journal of the American Chemical Society.

[2]  M. Krische,et al.  Enantioselective iridium-catalyzed carbonyl allylation from the alcohol oxidation level via transfer hydrogenation: minimizing pre-activation for synthetic efficiency. , 2009, Chemical communications.

[3]  M. Krische,et al.  Enantioselective allylation, crotylation, and reverse prenylation of substituted isatins: iridium-catalyzed C-C bond-forming transfer hydrogenation. , 2009, Angewandte Chemie.

[4]  M. Krische,et al.  Concise synthesis of the bryostatin A-ring via consecutive C-C bond forming transfer hydrogenations. , 2009, Organic letters.

[5]  G. O'Doherty,et al.  De Novo Asymmetric Syntheses of (+)-Goniothalamin, (+)-Goniothalamin oxide and 7,8-Bis-epi-Goniothalamin using Asymmetric Allylations. , 2009, Tetrahedron.

[6]  M. Krische,et al.  Elongation of 1,3-polyols via iterative catalyst-directed carbonyl allylation from the alcohol oxidation level. , 2009, Organic letters.

[7]  M. Krische,et al.  1,n-glycols as dialdehyde equivalents in iridium-catalyzed enantioselective carbonyl allylation and iterative two-directional assembly of 1,3-polyols. , 2009, Angewandte Chemie.

[8]  M. Krische,et al.  Enantioselective carbonyl reverse prenylation from the alcohol or aldehyde oxidation level employing 1,1-dimethylallene as the prenyl donor. , 2009, Journal of the American Chemical Society.

[9]  M. Krische,et al.  Catalytic carbonyl addition through transfer hydrogenation: a departure from preformed organometallic reagents. , 2009, Angewandte Chemie.

[10]  M. Krische,et al.  anti-Diastereo- and enantioselective carbonyl crotylation from the alcohol or aldehyde oxidation level employing a cyclometallated iridium catalyst: alpha-methyl allyl acetate as a surrogate to preformed crotylmetal reagents. , 2009, Journal of the American Chemical Society.

[11]  M. Krische,et al.  Formation of C-C Bonds via Catalytic Hydrogenation and Transfer Hydrogenation: Vinylation, Allylation, and Enolate Addition of Carbonyl Compounds and Imines. , 2010, Aldrichimica acta.

[12]  W. Roush,et al.  Total syntheses of (+)-tedanolide and (+)-13-deoxytedanolide. , 2008, Journal of the American Chemical Society.

[13]  Michael J. Krische,et al.  Enantioselective iridium-catalyzed carbonyl allylation from the alcohol or aldehyde oxidation level via transfer hydrogenative coupling of allyl acetate: departure from chirally modified allyl metal reagents in carbonyl addition. , 2008, Journal of the American Chemical Society.

[14]  M. Krische,et al.  Formation of C-C Bonds via Ruthenium Catalyzed Transfer Hydrogenation: Carbonyl Addition from the Alcohol or Aldehyde Oxidation Level. , 2008, Chemistry letters.

[15]  G. van Koten,et al.  Catalytic performance of symmetrical and unsymmetrical sulfur-containing pincer complexes: synthesis and tandem catalytic activity of the first PCS-pincer palladium complex. , 2008, Chemistry.

[16]  M. Krische,et al.  Enantioselective iridium-catalyzed carbonyl allylation from the alcohol or aldehyde oxidation level using allyl acetate as an allyl metal surrogate. , 2008, Journal of the American Chemical Society.

[17]  U. Eggert,et al.  The total synthesis of (+)-tedanolide--A macrocyclic polyketide from marine sponge Tedania ignis. , 2008, Chemistry.

[18]  Amos B. Smith,et al.  Total synthesis of (+)-tedanolide. , 2007, Journal of the American Chemical Society.

[19]  D. Hall.  Lewis and Brønsted Acid Catalyzed Allylboration of Carbonyl Compounds: From Discovery to Mechanism and Applications , 2007 .

[20]  I. Marek,et al.  Creation of quaternary stereocenters in carbonyl allylation reactions. , 2007, Chemical communications.

[21]  U. Eggert,et al.  The total synthesis of (+)-tedanolide. , 2006, Journal of the American Chemical Society.

[22]  Chan-Mo Yu,et al.  Regulation of Stereoselectivity and Reactivity in the Inter- and Intramolecular Allylic Transfer Reactions , 2006 .

[23]  W. Roush,et al.  Total synthesis of (+)-13-deoxytedanolide. , 2005, Journal of the American Chemical Society.

[24]  Richard E. Taylor,et al.  Total synthesis and stereochemical assignment of myriaporones 1, 3, and 4. , 2004, Angewandte Chemie.

[25]  F. Reyes,et al.  Total synthesis of natural myriaporones. , 2004, Angewandte Chemie.

[26]  D. Hall,et al.  Recent advances in the activation of boron and silicon reagents for stereocontrolled allylation reactions. , 2003, Angewandte Chemie.

[27]  S. Denmark,et al.  Catalytic enantioselective addition of allylic organometallic reagents to aldehydes and ketones. , 2003, Chemical reviews.

[28]  J. Tanaka,et al.  Umpolung of vinyloxiranes: regio- and stereoselectivity of the In/Pd-mediated allylation of carbonyl compounds. , 2001, The Journal of organic chemistry.

[29]  T. Miura,et al.  New Chiral Diphosphine Ligands Designed to have a Narrow Dihedral Angle in the Biaryl Backbone , 2001 .

[30]  S. Hashimoto,et al.  One-pot enantioselective synthesis of optically active homoallylic alcohols from allyl halides. , 2000, Chemical & pharmaceutical bulletin.

[31]  Yoshinori Yamamoto,et al.  SELECTIVE REACTIONS USING ALLYLIC METALS , 1993 .

[32]  Y. Masuyama,et al.  Palladium-catalyzed carbonyl allylation by allylic alcohols with stannous chloride , 1992 .

[33]  Y. Masuyama,et al.  Allylic alcohols as synthons of allylic carbanions. Palladium-catalyzed carbonyl allylation by allylic alcohols with tin dichloride , 1988 .

[34]  Y. Masuyama,et al.  Diastereoselectivity in carbonyl allylation by allylic carbonates using pdcl2(phcn)2-sncl2 system , 1988 .

[35]  Takashi Matsumoto,et al.  First total synthesis of mycinamicin IV and VII.: Successful application of new glycosidation reaction , 1988 .

[36]  O. Yonemitsu,et al.  Highly stereoselective total synthesis of tylonolide, the aglycon of the 16-membered macrolide antibiotic tylosin. II: Total synthesis of tylonolide by virtue of 4-methoxybenzyl and 3,4-dimethoxybenzyl protection , 1987 .

[37]  K. Tomooka,et al.  Stereocontrolled first total synthesis of mycinolide IV , 1987 .

[38]  O. Yonemitsu,et al.  Total synthesis of tylonolide, the aglycone of the 16-membered ring macrolide tylosin, from D-glucose. Selective application of MPM and DMPM protecting groups for hydroxy functions☆ , 1986 .

[39]  K. Tatsuta,et al.  TOTAL SYNTHESIS OF TYLOSIN , 1983 .

[40]  N. Lin,et al.  Bicyclo[2.2.1]heptanes in organic synthesis. Total synthesis of the 16-membered ring macrolide tylonolide hemiacetal: synthesis and coupling of the C(3)-C(9) and C(11)-C(17) fragments , 1982 .

[41]  S. Masamune,et al.  Synthesis of Tylonolide, The Aglycone of Tylosin , 1982 .

[42]  R. W. Hoffmann.  Diastereogenic Addition of Crotylmetal Compounds to Aldehydes , 1982 .

[43]  K. Nicolaou,et al.  Carbohydrates in organic synthesis. Synthesis of 16-membered-ring macrolide antibiotics. 6. Total synthesis of O-mycinosyltylonolide: coupling of key intermediates and macrocyclization , 1982 .

[44]  K. Tatsuta,et al.  Total synthesis of tylonolide, an aglycone of tylosin , 1982 .