10.1021/ja0672932.s001 David M. Hodgson David M. Hodgson Ying Kit Chung Ying Kit Chung Irene Nuzzo Irene Nuzzo Glòria Freixas Glòria Freixas Krystyna K. Kulikiewicz Krystyna K. Kulikiewicz Ed Cleator Ed Cleator Jean-Marc Paris Jean-Marc Paris Intramolecular Cyclopropanation of Unsaturated Terminal Epoxides and Chlorohydrins American Chemical Society 2007 TMP LTMP bicyclo Unsaturated Terminal Epoxides intramolecular cyclopropanation terminal epoxides epoxide formation synthesis cyclopropanation protocol Intramolecular Cyclopropanation bicyclic adducts bicyclic cyclopropanes stereoselective entry 2007-04-11 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Intramolecular_Cyclopropanation_of_Unsaturated_Terminal_Epoxides_and_Chlorohydrins/3013546 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 (+)-β-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation.