Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins.
Identifieur interne : 000148 ( PubMed/Curation ); précédent : 000147; suivant : 000149Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins.
Auteurs : David M. Hodgson [Royaume-Uni] ; Ying Kit Chung ; Irene Nuzzo ; Gloria Freixas ; Krystyna K. Kulikiewicz ; Ed Cleator ; Jean-Marc ParisSource :
- Journal of the American Chemical Society [ 0002-7863 ] ; 2007.
Descripteurs français
- KwdFr :
- MESH :
- synthèse chimique : Sesquiterpènes.
- Aldéhydes, Catalyse, Chlorohydrines, Composés époxy, Cyclopropanes, Heptanes, Hexanes, Isomérie, Sesquiterpènes, Structure moléculaire.
English descriptors
- KwdEn :
- MESH :
- chemical , chemical synthesis : Sesquiterpenes.
- chemical , chemistry : Aldehydes, Bicyclo Compounds, Chlorohydrins, Cyclopropanes, Epoxy Compounds, Heptanes, Hexanes, Sesquiterpenes.
- Catalysis, Isomerism, Molecular Structure.
Abstract
Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]hexan-2-ols via Sn-Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g-7.5 kg) synthesis of bicyclo[3.1.0]hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-beta-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation.
DOI: 10.1021/ja0672932
PubMed: 17373790
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pubmed:17373790Le document en format XML
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<front><div type="abstract" xml:lang="en">Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]hexan-2-ols via Sn-Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g-7.5 kg) synthesis of bicyclo[3.1.0]hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-beta-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation.</div>
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