Unexpected reactivity of acetylenic omega-ketoesters toward TBAF and t-BuOK; new cascade reactions affording allene and oxetane derivatives.

[reaction: see text]. The reactivity of acetylenic omega-ketoesters toward tetra-n-butylammonium fluoride and potassium tert-butoxide was studied. These cascade reactions proceeded smoothly and afforded either electrophilic allene derivatives or highly functionalized oxetane derivatives in moderate to high yields.

[1]  M. Miesch,et al.  Uncatalyzed, Solvent‐Free [2+2] Cycloaddition of Cyclic Ketene Trimethylsilyl Acetals with Electrophilic Acetylenes , 2000 .

[2]  M. Miesch,et al.  UNCATALYZED 2+2 CYCLOADDITION OF CYCLIC KETENETRIMETHYLSILYLACETALS WITH ELECTROPHILIC ACETYLENES , 1999 .

[3]  T. Taniguchi,et al.  Synthesis of polycyclic cyclobutane derivatives by tandem intramolecular Michael-aldol reaction under two complementary conditions: TBDMSOTf-Et3N and TMSI-(TMS)2NH , 1993 .

[4]  M. Miesch,et al.  The cyclobutenic way to triquinanes. Synthesis of (±) silphinene , 1991 .

[5]  L. Wessjohann,et al.  Tailoring the Reactivity of Small Ring Building Blocks for Organic Synthesis , 1990 .

[6]  M. Miesch,et al.  The bicyclo [2.1.0] Pentane way to the diquinane alcohol part of natural triquinanes. A high yield access starting from trimethylsilyloxycyclopentene. , 1990 .

[7]  N. S. Vyazankin,et al.  Tetrahedron report number 234 Synthetic aspects of the use of organosilicon compounds under nucleophilic catalysis conditions , 1988 .

[8]  H. Wong,et al.  The application of cyclobutane derivatives in organic synthesis , 1986 .

[9]  T. Sakai,et al.  Malonate anion induced Favorskii-type rearrangements. 2. Reaction of acyclic .alpha.-haloketones with carbanions leading to cyclopropanols , 1981 .

[10]  J. Clark.  Fluoride ion as a base in organic synthesis , 1980 .

[11]  J. Lehn,et al.  Ab initio study of nucleophilic addition to a carbonyl group , 1974 .

[12]  Jack D. Dunitz,et al.  Stereochemistry of reaction paths at carbonyl centres , 1974 .