Carbanion induced synthesis of annulated unsymmetrical biaryls through ring transformation of 2H-pyran-2-oneCentral Drug Research Institute communication no. 6207

An innovative and convenient one-pot synthesis of unsymmetrical macrocyclic biaryls (3, 5 and 8), dibenzo[a,c]cycloheptenes (10), 3,4-dihydro-2(1H)-naphthones (15), tetrahydroisoquinolines (18), dihydro-1H-isothiochromenes (20), benzo[c]thiochromenes (22) and 2,3-dihydro-1-benzothiophenes (24) is described. These compounds are obtained through base-catalyzed ring transformation reactions of suitably functionalized 2H-pyran-2-ones (1,6) by a carbanion, generated from cycloalkanone (2,4,7), benzosuberone (9), cyclohexanedione monoketal (12), 4-piperidone (17), tetrahydrothiopyran-4-one (19), thiochroman-4-one (21) or tetrahydrothiophene-3-one (23).

[1]  B. Jensen,et al.  A concise synthesis of 1-substituted-2-tetralones by selective diol dehydration leading to ketone transposition , 2000 .

[2]  C. Gill,et al.  Synthesis of 5,8‐Dimethyl‐2‐tetralone, an Intermediate for Occidol. , 1999 .

[3]  R. Larock,et al.  Carbocycle Synthesis via Carbopalladation of Nitriles , 1999 .

[4]  S. Chaki,et al.  Design, synthesis, structure-activity relationships, and biological characterization of novel arylalkoxyphenylalkylamine sigma ligands as potential antipsychotic drugs. , 1999, Journal of Medicinal Chemistry.

[5]  K. Y. Koltunov,et al.  Ionic Hydrogenation of 2‐Naphthol and 1,7‐Dihydroxynaphthalene with Cyclohexane in the Presence of Aluminum Halogenides. , 1999 .

[6]  B. Ranu,et al.  Indium(III) Chloride-Promoted Rearrangement of Epoxides: A Selective Synthesis of Substituted Benzylic Aldehydes and Ketones , 1998 .

[7]  D. Budac,et al.  Excited state carbon acid dissociation and competing photorearrangements of 5H-dibenzo[a,c]cycloheptene derivatives , 1996 .

[8]  D. Pryde,et al.  Synthesis of 2-tetralones via a novel 1,2-carbonyl transposition of 1-tetralones , 1996 .

[9]  B. Kirkiacharian,et al.  Hydroborations: A New Route for the Preparation of 1-Alkyl- (or Aryl) 2-Tetralones , 1993 .

[10]  M. Meegan,et al.  Synthesis and antifungal activity of some 2-aryl-3-hydroxymethylbenzo [b] thiophenes , 1992 .

[11]  P. Wan,et al.  Photochemistry of phenoxybenzyl alcohols in aqueous solution: photosolvolysis vs. photorearrangement to 6H-dibenzo[b,d]pyrans , 1991 .

[12]  A. Citterio,et al.  Polar effects in the decomposition of bis(3-alkoxyaroyl) peroxides. Synthesis of 8-alkoxy-6H-dibenzo[b,d]pyran-6-ones , 1990 .

[13]  W. Roth,et al.  Inversionsbarrieren Ortho,ortho′‐verbrückter Biphenyle , 1990 .

[14]  A. Brossi,et al.  Deaminocolchinyl Methyl Ether: Synthesis from 2,3,4,4′‐Tetramethoxybiphenyl‐2‐carbaldehyde. Comparison of antitubulin effects of deaminocolchinyl methyl ether and dehydro analogs , 1989 .

[15]  R. Noyori.  Centenary Lecture. Chemical multiplication of chirality: science and applications , 1989 .

[16]  R. Miller,et al.  Regiospecific synthesis of isoquinoline alkaloids. Use of arylsilanes in directed pictet-spengler cyclizations , 1988 .

[17]  A. McPhail,et al.  A novel synthesis of cis-1-[[6-chloro-3-[(2-chloro-3-thienyl)methoxy]-2,3-dihydrobenzo[b]thien-2-yl]methyl]1h-imidazole : A new class of azole antifungal agents , 1988 .

[18]  J. Dunn,et al.  Analgetic and antiinflammatory 7-aroylbenzofuran-5-ylacetic acids and 7-aroylbenzothiophene-5-ylacetic acids. , 1986, Journal of Medicinal Chemistry.

[19]  P. Wyman,et al.  7-Aroyl-2,3-dihydrobenzo[b]furan-3-carboxylic acids and 7-benzoyl-2,3-dihydrobenzo[b]thiophene-3-carboxylic acids as analgesic agents. , 1986, Journal of Medicinal Chemistry.

[20]  Y. Kai,et al.  Synthesis, structure and reactivities of [6]paracyclophanes , 1986 .

[21]  L. W. Jenneskens,et al.  Scope and Limitations of the Flash Vacuum Thermolysis Approach to Small [n]Paracyclophanes. , 1986 .

[22]  M. Pomerantz,et al.  Thermal reorganizations of 1,2:3,4-dibenzotropilidene (5H-dibenzo[a,c]cycloheptene), 7,7'-bi(1,2:3,4-dibenzotropyl) [5,5'-bi(5H-dibenzo[a,c]cycloheptenyl)], and the 1,2:3,4-dibenzotropyl (dibenzo[a,c]cycloheptenyl) free radical , 1984 .

[23]  Frantis˛ek Mikes˛,et al.  Resolution of optical isomers by high-performance liquid chromatography , 1978 .

[24]  N. Heindel,et al.  Thianaphthen-2-one chemistry. I. Synthesis of 6H-benzothieno[3,2-c][1]benzopyran-6-ones (11-thiacoumestans) , 1975 .

[25]  R. Dodson,et al.  Polycyclic Compounds. I. The Reimer-Tiemann Reaction with 1-Alkyl-2-naphthols , 1951 .

[26]  J. C. Cavagnol,et al.  Syntheses in the Direction of Morphine. II.1 Some Intermediates and Model Compounds , 1950 .

[27]  L. Ruzicka,et al.  Zur Kenntnis des Kohlenstoffringes. Über cis-3.4-Polymethylen-cyclohexanone , 1947 .