Kinetic and thermodynamic control of axial chirality in biaryl-derived fused oxazolidine lactams exploiting a centre-axis relay of unit efficiency.

The condensation of a 2-substituted-2-aminoethanol with methyl 2'-formylbiphenyl-2-carboxylate produces only two of the four possible axially chiral 6,7-dihydrodibenz[c,e]oxazolo[3,2-a]azepin-9(4bH)-ones (fused oxazolidine lactams), with kinetically controlled diastereoisomer ratios of up to 96 : 4. Within each lactam product the central chirality of the oxazolidine-fused benzylic position C(4b) is relayed to the biaryl axis with unit efficiency, the mis-matching of these stereogenic elements being prohibited due to strain, as predicted by molecular mechanics calculations. Diastereoisomeric lactam pairs can be equilibrated by heating with acid, and under these thermodynamic conditions reversed diastereoisomer ratios of up to 26 : 74 are observed.

[1]  G. Hilt,et al.  A Modular Approach for the Synthesis of Dibenzoazepine Derivatives , 2006 .

[2]  T. Wallace.  Biaryl synthesis with control of axial chirality. , 2006, Organic & biomolecular chemistry.

[3]  E. Yashima,et al.  Dynamic Axial Chirality Control of a Carboxybiphenol through Acid–Base Interaction , 2006 .

[4]  C. Papamicaël,et al.  Meyers’ bicyclic lactam formation under mild and highly stereoselective conditions , 2005 .

[5]  G. Bringmann,et al.  Atroposelective synthesis of axially chiral biaryl compounds. , 2005, Angewandte Chemie.

[6]  D. J. Edwards,et al.  Fine-tuning of biaryl dihedral angles: structural characterization of five homologous three-atom bridged biphenyls by X-ray crystallography. , 2005, Acta crystallographica. Section B, Structural science.

[7]  M. Penhoat,et al.  Novel extension of Meyers' methodology: stereoselective construction of axially chiral 7,5-fused bicyclic lactams. , 2003, The Journal of organic chemistry.

[8]  B. Borhan,et al.  Direct lactonization of alkenols via osmium tetroxide-mediated oxidative cleavage. , 2003, Organic letters.

[9]  S. James,et al.  Identification of a highly effective asymmetric phase-transfer catalyst derived from α-methylnaphthylamine , 2003 .

[10]  D. J. Edwards,et al.  Complementary kinetic and thermodynamic resolution of a chiral biaryl axis. , 2003 .

[11]  M. Karplus,et al.  Alkaline Hydrolysis of Amide Bonds: Effect of Bond Twist and Nitrogen Pyramidalization , 2003 .

[12]  A. Alexakis,et al.  Enantioselective Copper-Catalysed Conjugate Addition , 2002 .

[13]  K. Mikami,et al.  Tropos or Atropos? That Is the Question! , 2002 .

[14]  M. Kameda,et al.  Conformationally flexible, chiral quaternary ammonium bromides for asymmetric phase-transfer catalysis. , 2002, Angewandte Chemie.

[15]  A. Meyers,et al.  Chiral Non-Racemic Bicyclic Lactams. Auxiliary-Based Asymmetric Reactions , 2000 .

[16]  Z. Zhang,et al.  Synthesis of chiral bisphosphines with tunable bite angles and their applications in asymmetric hydrogenation of beta-ketoesters. , 2000, The Journal of organic chemistry.

[17]  M. Orozco,et al.  Synthesis of enantiopure trans-3,4-disubstituted piperidines. An enantiodivergent synthesis of (+)- and (-)-paroxetine. , 2000, The Journal of organic chemistry.

[18]  I. Císařová,et al.  Intramolecular transfer of axial to central chirality in the strecker reaction. Synthesis and stereochemistry of 5,7-dicyano-6,7-dihydro-5H-dibenz[c,e]azepines , 1999 .

[19]  U. Berg,et al.  The Absolute Configuration of Colchicine by Correct Application of theCIP Rules , 1999 .

[20]  E. Glendening,et al.  Resonance in Formamide and Its Chalcogen Replacement Analogues: A Natural Population Analysis/Natural Resonance Theory Viewpoint , 1997 .

[21]  P. Renaud,et al.  Preparation of ortho-aryl-benzaldehyde derivatives via free-radical ipso-substitution of an amidomethyl group , 1997 .

[22]  B. Decroix,et al.  Synthesis of dibenz[c,e]azepine and benzo[e]thieno[c]azepine via, N-acyliminium ion cyclization , 1997 .

[23]  David A. Fletcher,et al.  The United Kingdom Chemical Database Service , 1996, J. Chem. Inf. Comput. Sci..

[24]  J. Bosch,et al.  Chiral precursors for the synthesis of enantiomerically pure piperidines. Total synthesis of (R)-(-)-coniine , 1994 .

[25]  D. Romo,et al.  Chiral non-racemic bicyclic lactams. Vehicles for the construction of natural and unnatural products containing quaternary carbon centers. , 1991 .

[26]  A. Brossi,et al.  Alfred Burger award address. Bioactive alkaloids. 4. Results of recent investigations with colchicine and physostigmine. , 1990, Journal of medicinal chemistry.

[27]  C. George,et al.  aS,7S‐absolute configuration of natural (−)‐colchicine and allocongeners , 1990, FEBS letters.

[28]  Liren Huang,et al.  Acylation of 2,4-disubstituted thiazolidines and oxazolidines. Concomitant epimerization at C-2. , 1987 .

[29]  T. Araki,et al.  Photochemical Electron-transfer Reactions of Biphenyl-2,2′-dicarboximide and Naphthalene-1,8-dicarboximide with Olefin. Dependence of the Reaction Course on the Structure of the Aromatic Imide , 1985 .

[30]  D. Seebach,et al.  α-alkylation of serine with self-reproduction of the center of chirality , 1984 .

[31]  Daniel Swern,et al.  Activated Dimethyl Sulfoxide: Useful Reagents for Synthesis , 1981 .

[32]  K. Schlögl,et al.  Biphenyl(tricarbonylchrom)‐Komplexe, V. Optisch aktive Tricarbonylchrom‐Komplexe der Diphensäure und ihrer Derivate — Enantiomerenreinheit, Circulardichroismus und absolute Konfiguration , 1980 .

[33]  W. C. Still,et al.  Rapid chromatographic technique for preparative separations with moderate resolution , 1978 .

[34]  R. Labriola,et al.  HYDRAZIDES OF DIPHENIC AND 4-NITRODIPHENIC ACIDS AND SOME OF THEIR REACTIONS , 1943 .

[35]  A. Meyers,et al.  The synthesis of (S)-(+)-gossypol via an asymmetric Ullmann coupling , 1997 .

[36]  K. Higashiyama,et al.  Diastereoselective addition of organometallic reagents to chiral imines and 1,3-oxazolidines , 1992 .

[37]  M. Feigel,et al.  A macrocycle containing two biphenyl and two alanine subunits, synthesis and conformation in solution , 1989 .

[38]  H. Kalchhauser,et al.  Biphenyl tricarbonylchromium complexes. Part 7. Preparation, static and dynamic stereochemistry of mono- and bis-tricarbonylchromium complexes of o,o′-bridged biphenyls , 1983 .

[39]  K. Schlögl,et al.  Stereochemie von Metallocenen, 44. Mitt.: Darstellung und Konfiguration von Tricarbonylchrom-Komplexen der Diphensäure und ihrer Derivate 3. Mitt. über Biphenyl-tricarbonylchrom-Komplexe , 1980 .

[40]  E. F. M. Stephenson.  Heterocyclic nitrogen compounds. Part IV. Further condensations with aldehydic acids and diamines , 1954 .