Superbases for organic synthesis

  title={Superbases for organic synthesis},
  author={Manfred Schlosser},
  journal={Pure and Applied Chemistry},
  pages={1627 - 1634}
  • M. Schlosser
  • Published 1988
  • Chemistry
  • Pure and Applied Chemistry
A review with 70 refs. LICKOR mixts. of organolithium reagents and bulky potassium alcoholates allow the smooth metalation and subsequent electrophilic substitution of low acidity hydrocarbons, in particular olefins. The allylpotassium intermediates exhibit peculiar conformational preferences which can be exploited in novel stereoselective carbon-carbon linking reactions. A few syntheses of simple natural products illustrate the method. A tentative explanation is given for the superior… Expand
Facile isomerization of oxiranes to allyl alcohols by mixed metal bases
Abstract The mixture of lithium diisopropylamide and potassium tert-butoxide (“LIDAKOR reagent”) promotes smooth ring opening of oxiranes to afford allyl alcohols with good to excellent yields.Expand
A one-pot synthesis of ibuprofene involving three consecutive steps of superbase metalation
A one-pot reaction sequence consisting of three consecutive metalation and electrophilic substitution stages starting with p-xylene leads to 2-(4-isobutylphenyl)propanoic acid with a 52% overallExpand
Pyridine elaboration through organometallic intermediates: regiochemical control and completeness.
This approach relies on organometallic methods, which are both efficacious and extremely flexible as far as the substitution site and the product structure are concerned (86 references). Expand
On the direct metalation of isoprene
Abstract Isoprene has been metalated in tetrahydrofuran with an excess of sterically hindered potassium dialkylamides, prepared by combining equimolar amounts of the corresponding lithium amide andExpand
Two homoallyl/cyclopropylalkyl rearrangements accompanying a Wolff-Kishner type reduction
Conceived as a model study for the enantioselective synthesis of the natural product (S)-bakuchiol, the deoxygenation of a recently described trishomoallyl alc. was attempted using the KabalkaExpand
Metalated fluoropyridines and fluoroquinolines as reactive intermediates: new ways for their regioselective generation
The mixt. of lithium diisopropylamide and potassium tert-butoxide (LIDA-KOR reagent) is a powerful base which can be advantageously employed for the regioselective deprotonation of fluoropyridinesExpand
Structural Motifs of Alkali Metal Superbases in Non‐coordinating Solvents
  • J. Klett
  • Medicine, Chemistry
  • Chemistry
  • 2020
New insights into the nature of the reactive species could not be pinned down either for this composition or for similar mixtures with comparable high reactivity, leading to advanced and more detailed conclusions about the interplay of the involved components. Expand
Isopulegol as a Model Compound: Metalation and Substitution of an Allylic Position in the Presence of an Unprotected Hydroxy Function
When treated with BuLi and KOCMe3 for 2 h at 0 Deg in hexane, the unsatd. monoterpenic alc. isopulegol is simultaneously deprotonated at the hydroxy function and the allylic Me group. The metaloxyExpand
Sodium and Potassium
This chapter discusses the general aspects of the chemistry of organoalkali reagents mainly focusing on the achievements of the last decade. Due to the difficulty in their preparation and handling,Expand
The preparation of pure allyl- and benzyl-type organoalkali intermediates via organotin compounds
Superbase metalation of alkenes or alkylbenzenes and subsequent condensation with trialkylstannyl chloride affords allyl- or benzyl-type organotin compds. that can be isolated in pure form. TreatmentExpand


Enantiomeric Z- and E-crotyldiisopinocampheylboranes. Synthesis in high optical purity of all four possible stereoisomers of .beta.-methylhomoallyl alcohols
Synthese des 4 stereoisomeres du methyl-3 pentene-4 ol-2 par reaction de (butene-2 diisopinocamphenyl) borane avec l'acetaldehyde
A diastereoselective synthesis of both quercus lactone isomers employing allyl-type organometallics as key intermediates
Consecutive treatment of endo-butenylpotassium or endo-1-(tetrahydropyranyloxy)-exo-butenyllithium with FB(OMe)2 and pentanal at -75 Deg affords an erythro- and, threo-adduct, resp., which onExpand
Nuclear Magnetic Resonance Spectroscopy. The Structure of Butenylmagnesium Bromide
Crotyl bromide and α-methylallyl bromide each react with magnesium in ether to yield the same butenyl Grignard reagent, which conceivably could be crotylmagnesium bromide (I), α-methylallyl-magnesiumExpand
Haltermann, I
  • Chem. Soc
  • 1986
By the way, the superbase also metalates N,N,N:N’-tetramethylethyleneamine (yields of derivatives up to 45%, L
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