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.