78710-80-2Relevant academic research and scientific papers
Base-Mediated Radical Borylation of Alkyl Sulfones
Huang, Mingming,Hu, Jiefeng,Krummenacher, Ivo,Friedrich, Alexandra,Braunschweig, Holger,Westcott, Stephen A.,Radius, Udo,Marder, Todd B.
, (2021/12/02)
A practical and direct method was developed for the production of versatile alkyl boronate esters via transition metal-free borylation of primary and secondary alkyl sulfones. The key to the success of the strategy is the use of bis(neopentyl glycolato) diboron (B2neop2), with a stoichiometric amount of base as a promoter. The practicality and industrial potential of this protocol are highlighted by its wide functional group tolerance, the late-stage modification of complex compounds, no need for further transesterification, and operational simplicity. Radical clock, radical trap experiments, and EPR studies were conducted which show that the borylation process involves radical intermediates.
Lithium-titanium exchange of tertiary α-sulfonyl carbanions: Synthesis, structure, dynamics and reactivity of bis(1-sulfonylalkyl) titaniums
Hess, Thomas,Raabe, Gerhard,Gais, Hans-Joachim
, p. 7134 - 7147 (2015/03/04)
Lithium-titanium exchange of tertiary α-sulfonyl carbanions with ClTi(OiPr)3 and Cl2Ti(OiPr)2 in diethyl ether gave bis(1-sulfonylalkyl) titaniums and not the corresponding (1-sulfon-ylalkyl) titaniums. X-ray crystal structure analysis of di(iso-propoxy) bis[1-(phenylsulfonyl) cyclobutyl]titanium and di-(isopropoxy) bis[1-(phenylsulfonyl) isopropyl]titanium showed asymmetric distorted octahedral complexes, having hexaco-ordinate Ti atoms, two C-Ti bonds, four Ti-O bonds, and two four-membered Ti-O-S-Cα rings. According to 1H NMR spectroscopy bis(1-sulfonylcycloalkyl) titaniums are non-flux-ional at room temperature. This suggests that chiral bis(1-sulfonylalkyl) titaniums should be configurationally stable. The bis(1-sulfonylalkyl) titaniums are stable at room temperature towards β-H elimination. They selectively add to benzaldehyde in the presence of acetophenone but do not react with methyl iodide. The reaction of tertiary acyclic α-sulfonyl carbanions with ClTi(OiPr)3 in tetrahydrofuran (THF) gives different titanium derivatives with unspecified structures, which not only selectively react with benzaldehyde in the presence of acetophenone but are also alkylated by methyl iodide.
A new stereoselective synthesis of (±)-grandisol based on the remote alkylation protocol
Monteiro, Hugo J.,Stefani, Helio A.
, p. 2659 - 2663 (2007/10/03)
A new stereoselective synthesis of (±)-grandisol (1a) has been developed. The synthesis starts with a simple cyclobutyl derivative to which the methyl group and the 1,2-cis disposed side chains were appended through a remote alkylation protocol.
Formation of symmetrical alkenes by homocoupling of metallated sulfones under nickel catalysis
Gai, Yonghua,Julia, Marc,Jean-Noe,Verpeaux
, p. 805 - 816 (2007/10/03)
Summary -Allylic sulfones undergo a coupling reaction with organometallic compounds (Mg or Li) not only with copper catalysts but also with iron or nickel salts. With 7,7-disubstituted allylic sulfones and also saturated aliphatic sulfones, however, another reaction was observed whereby two molecules of the starting sulfone are coupled to give symmetrical alkenes. The scope of this reaction was investigated. Elsevier.
Reductive Lithiation of Bis-Phenylsulfones
Mioskowski, Charles
, p. 5437 - 5440 (2007/10/02)
Reductive cleavage of geminal bis-phenylsulfones using lithium naphthalenide in THF at -78 degC selectively affords α-sulfonyl carbanions which participate in typical reaction with electrophiles. - Key words: desulfonylation, lithium naphthalenide, alkyla
Bridgehead Reactivity, Nucleophilic and Radical Additions, and Lithium Aluminum Hydride Reduction of 1-(Arylsulfonyl)bicyclobutanes: General Access to Substituted, Functionalized Cyclobutanes. Syntheses of (+/-)-Citrilol Acetate, (+/-)-Junionone, and the
Gaoni, Yehiel,Tomazic, Alenka
, p. 2948 - 2957 (2007/10/02)
A general approach to the synthesis of a wide range of substituted cyclobutane derivatives is based on two specific reactions of 1-(arylsulfonyl)bicyclobutanes (1) and on some general reactions of the bicyclobutane ring systems.One specific cyclobutane fo
ARYL CYCLOBUTYL SULFONES BY REDUCTION OF 1-ARYLSULFONYLBICYCLOBUTANES WITH LITHIUM ALUMINIUM HYDRIDE. SYNTHESIS OF RACEMIC JUNIONONE
Gaoni, Yehiel
, p. 5219 - 5220 (2007/10/02)
Cyclobutyl sulfones are obtained by reduction of bicyclobutyl sulfones with lithium aluminium hydride and these may be used in further synthetic transformations, as illustrated by the synthesis of rac-junionone.
γ- and δ-epoxy sulfones. Formation of different ring-sized products upon reaction with CH3MgI or LiN2
Decesare, John M.,Corbel, Bernard,Durst, Tony,Blount, John F.
, p. 1415 - 1424 (2007/10/02)
γ-Epoxy sulfones in which the epoxide function is terminal yield cyclopropylmethanol derivatives on reaction with methylithium or lithium diisopropylamide.In contrast, treatment of these epoxides with two equivalents of CH3MgI gives only cis-3-phenylsulfonylcyclobutanols.The cis-relationship between the OH and sulfonyl groups was proven in one instance by an X-ray stucture determination.Inernal γ-epoxy sulfones yield cyclopropylmethanols with all bases studied.All δ-epoxy sulfones studied furnished cis-3-phenylsulfonylcyclopentanols upon reaction with the Grignard reagent.These same epoxides gave either cyclopentanols or noncyclic products upon reaction with LDA; no cyclobutane ring containing products were obtained contrary to the expectations based on Stork's results with the corresponding epoxy nitriles (ref. 2).The mechanism of the Grignard-mediated reaction involves epoxide opening by iodide ion, α-sulfonyl Grignard formation, and, finally, cyclization.When LDA or CH3Li is used the products are formed by an intramolecular SN2 opening of the epoxide by an α-lithio sulfone.
