1‐Lithio‐1‐methoxycyclopropane

[75697-62-0] C4H7LiO (MW 78.05) InChI = 1S/C4H7O.Li/c1-5-4-2-3-4;/h2-3H2,1H3; InChIKey = WHIBJYNFKQDVDM-UHFFFAOYSA-N (synthesis of 2-vinylcyclobutanones,2 which are intermediates in the synthesis of higher-membered rings via ring expansion3) Solubility: sol THF, in which solvent it is prepared. Preparative Methods: from 1-methoxy-1-phenylthiocyclopropane4 via reductive lithiation with Lithium 4,4′-Di-tert-butylbiphenylide (LDBB) or Lithium 1-(Dimethylamino)naphthalenide (LDMAN) in THF at −78 °C.5 Alternatively, a similar reagent, 1-ethoxy-1-lithiocyclopropane, is obtained by lithium–tin and lithium–bromine exchange reactions of 1-ethoxy-1-(tri-n-butylstannyl)cyclopropane and 1-bromo-1-ethoxycyclopropane, respectively.6 Handling, Storage, and Precautions: presumed to be unstable and is used immediately for further transformations. α-Metalated ethers undergo Wittig rearrangement7 and/or carbenoid reactions.8

[1]  P. Kocieňski,et al.  Synthetic applications of metallate rearrangements , 1990 .

[2]  L. Brockunier,et al.  Efficient synthesis of 2-vinylcyclobutanones by the rearrangement of 1-methoxy-1-cyclopropylcarbinols under neutral conditions , 1989 .

[3]  A. Krief.  Synthesis and synthetic applications of 1-metallo-1-selenocyclopropanes and -cyclobutanes and related 1-metallo-1-silylcyclopropanes , 1987 .

[4]  T. Nakai,et al.  [2,3]-Wittig sigmatropic rearrangements in organic synthesis , 1986 .

[5]  B. Trost.  Strain and reactivity: Partners for selective synthesis , 1986 .

[6]  R. Gadwood,et al.  Generation of (1-alkoxycyclopropyl)lithium reagents , 1985 .

[7]  T. A. Spencer,et al.  A novel 1,4 cyclohexenone annulation , 1985 .

[8]  T. Lyle,et al.  Photochemical reactions, 135th communication Photochemistry of Homoconjugated Cyclobutanones. II. Decisive Effect of gem‐ Dimethyl Substitution on the Course of the Oxa‐di‐π‐methane Rearrangement , 1984 .

[9]  M. Bhupathy,et al.  A practical method for using alkoxide-accelerated vinylcyclobutane ring expansions in the synthesis of six-membered rings. Unexpected orbital symmetry allowed and forbidden 1,3-sigmatropic rearrangements , 1983 .

[10]  A. Krief,et al.  Regioselective syntheses of polyalkyleted cyclopentanones , 1982 .

[11]  T. Cohen,et al.  Cyclopentenone and cyclohexenone annulations via acid-catalyzed 1,2- and 1,3-acyl migration of 2-vinylcyclobutanones. Rearrangement route to spiro- and angularly substituted fused-cyclopentenones. , 1981 .

[12]  T. Cohen,et al.  A synthesis of 2-vinylcylobutanones using 1-methoxycyclopropyllithium reagents , 1981 .

[13]  T. Cohen,et al.  A general preparative method for .alpha.-lithioethers and its application to a concise, practical synthesis of brevicomin , 1980 .

[14]  Kazuhiko Tanaka,et al.  A simple, highly versatile synthesis of cyclopropyl phenyl sulfides. , 1980 .

[15]  A. Krief,et al.  Regiospecific synthesis of alkylidene cyclopropanes , 1980 .

[16]  B. Trost,et al.  Lithiation of cyclopropyl and 2-methylcyclopropyl phenyl sulfides. Addition to carbonyl partners , 1977 .

[17]  D. Seebach,et al.  Cyclobutanones from 1‐Bromo‐1‐lithiocyclopropanes and Ketones , 1974 .