63662-71-5Relevant academic research and scientific papers
Diradical-promoted (n + 2 - 1) ring expansion: An efficient reaction for the synthesis of macrocyclic ketones
Rueedi, Georg,Oberli, Matthias A.,Nagel, Matthias,Hansen, Hans-Jurgen
, p. 3179 - 3181 (2007/10/03)
(Chemical Equation Presented) A diradical-promoted (n + 2 - 1) ring expansion reaction based on vinyl side chain insertion (+2C) and decarbonylation (-1C) has been developed. Flash vacuum pyrolysis (FVP) of medium- and large-ring 2-trimethylsilyloxy-2-vinyl-cycloalkanones at 500-600°C affords the one-carbon ring-expanded cycloalkanones in good yields. Methyl groups on the vinyl moiety are transformed regiospecifically as corresponding α- and β-substituents, respectively. 2-Ethynyl precursor analogues react in a manner similar to give α,β-unsaturated cyclic ketones.
Short and versatile two-carbon ring expansion reactions by thermo-isomerization: Novel straightforward synthesis of (±)-muscone, nor- and homomuscones, and further macrocyclic ketones
Nagel, Matthias,Hansen, Hans-Jürgen,Fráter, Georg
, p. 280 - 284 (2007/10/03)
Thermo-isomerization of 1-vinyl substituted medium-and large-ring cycloalkanol derivatives in a flow reactor system at temperatures of 600°C to about 650°C leads directly to the ring-expanded macrocyclic ketones. Alkyl substituents at the vinylic moiety are transferred locospecifically to the ring-expanded ketone as corresponding α-, and β-substituents, respectively. This novel thermal 1,3-C shift reaction therefore provides a new access to short syntheses of many alkyl-substituted macrocyclic ketone derivatives [e.g. (±)-muscone and analogues] in a systematic manner.
The synthesis of 14-membered macrocyclic ethers
Clyne, Dean S.,Weiler, Larry
, p. 13659 - 13682 (2007/10/03)
As part of an ongoing study of the chemistry of macrocyclic compounds, 14-membered macrocyclic ethers with a variety of methyl substitution patterns were synthesized. The preparation of these macrocyclic ethers involved either the Baeyer-Villiger ring expansion of a cyclic ketone, or the macrolactonization of a hydroxy acid to give a lactone. The lactone carbonyl was removed either by conversion to an intermediate thionolactone obtained by reaction with Lawesson's reagent and reduction, or by direct reduction using a boron trifluoride etherate mediated sodium borohydride reaction.
New Method for Generation of β-Oxido Carbenoid via Ligand Exchange Reaction of Sulfoxides: A Versatile Procedure for One-Carbon Homologation of Carbonyl Compounds
Satoh, Tsuyoshi,Itoh, Norifumi,Gengyo, Kaoru,Takada, Sae,Asakawa, Naoyuki,et al.
, p. 11839 - 11852 (2007/10/02)
A new procedure for one-carbon homologation of carbonyl compounds is described.The method is based on the rearrangement of β-oxido carbenoid which is generated via the ligand exchange reaction of the sulfinyl group of α-chloro β-hydroxy sulfoxide with tert-butyllithium.Addition of the carbanion of aryl 1-chloroalkyl sulfoxides to carbonyl compounds gave the adducts in good yields.The β-oxido carbenoid rearrangement of the adducts gave one-carbon homologated carbonyl compounds having an α-alkyl substituent.A similar reaction of the adducts derived from carbonyl compounds with chloromethyl p-tolyl sulfoxide yielded a procedure for a methylene insertion.The stereochemistry of the β-oxido carbenoid rearrangenment is also discussed.
A novel method for generation of carbenoid from α-chloro sulfoxides: A new and versatile procedure for one-carbon homologation of carbonyl compounds to carbonyl compounds having an α-alkyl substituent
Satoh, Tsuyoshi,Itoh, Norifumi,Gengyo, Kaoru,Yamakawa, Koji
, p. 7543 - 7546 (2007/10/02)
Addition of the carbanion of 1-chloroalkyl p-tolyl sulfoxides to carbonyl compound gave the adducts, which were treated with a base followed by t-butyllithium to afford one-carbon homologated carbonyl compounds having an alkyl group at the α-position, via the β-oxido carbenoids, in moderate to good yields.
REACTIVITY OF (3-CHLORO-2-METHYLENECYCLOALKYL)PALLADIUM CHLORIDE DIMERS: PD-ALLYL CLEAVAGE, SYNTHESIS OF (+/-)-13-METHYLTRIDECANOLIDE
Donaldson, William A.,Taylor, Barbara S.
, p. 4163 - 4166 (2007/10/02)
The reactions of the title compounds under cleavage conditions affords the corresponding cycloalkenes as the major product.This methodology was used in the synthesis of 13-methyltridecanolide from cyclododecene.
