52306-27-1

Upstream product

• 75-11-6 diiodomethane 
• 93-55-0 1-phenyl-propan-1-one 
• 87456-64-2 α-tosyloxypropiophenone 
• 31729-70-1 bis(iodozinc)methane 
• 93-58-3 benzoic acid methyl ester 
• 920-39-8 isopropylmagnesium bromide 
• 93-89-0 benzoic acid ethyl ester 
• 927-77-5 n-propylmagnesium bromide 
• 66323-99-7 trimethyl[(Z)-(1-phenyl-1-propenyl)oxy]silane 

Downstream Products

• 136068-08-1 S-phenyl 3-methyl-5-oxo-5-phenylpentanethioate 
• 1226-91-1 3-methyl-1,5-diphenyl-pentane-1,5-dione 

Relevant academic research and scientific papers

The Cyclopropane Ring as a Reporter of Radical Leaving-Group Reactivity for Ni-Catalyzed C(sp3)-O Arylation

The ability to understand and predict reactivity is essential for the development of new reactions. In the context of Ni-catalyzed C(sp3)-O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C(sp3)-O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the ring-opened product is obtained under polar (2e) conditions, and the ring-closed product is obtained under radical (1e) conditions. Mechanistic studies demonstrate that the optimal leaving group is redox-active and are consistent with a Ni(I)/Ni(III) catalytic cycle. The optimized reaction conditions are also used to synthesize a number of arylcyclopropanes, which are valuable pharmaceutical motifs.

Stereospecific construction of chiral tertiary and quaternary carbon by nucleophilic cyclopropanation with bis(iodozincio)methane

The reaction of a ketone having a leaving group at the aposition, such as a,bepoxy ketone or asulfonyloxy ketone, with bis(iodozincio) methane affords a zinc alkoxide of cyclopropanol. The reaction proceeds by nucleophilic addition of the dizinc to the carbonyl group and a sequential intramolecular nucleophilic substitution of the introduced iodozinciomethyl group to the adjacent electrophilic carbon that has a leaving group. When an optically active a,β-epoxy ketone or asulfonyloxy ketone is treated with the dizinc, a zinc alkoxide of cyclopropanol having a chiral tertiary or quaternary carbon in the cyclopropane ring is obtained, and the obtained zinc alkoxide of cyclopropanol acts as a chiral ho-moenolate. When it is treated with an electrophile in the presence of copper cyanide, it gives an optically active a-tertiary or -quaternary ketone that retains high optical purity.

Transformation of zirconocene-olefin complexes into zirconocene allyl hydride and their use as dual nucleophilic reagents: Reactions with acid chloride and 1,4-diketone

Zirconocene-olefin complexes Cp2Zr(H2C=CHR), prepared in benzene-THF at 0 °C, react with acid chlorides to provide homoallylic alcohols. The key is an equilibrium between the zirconocene-olefin complexes and the corresponding zircono

Mechanism of the Kulinkovich Cyclopropanol Synthesis: Transfer-Epititanation of the Alkene in Generating the Key Titanacyclopropane Intermediate

An investigation of the Kulinkovich cyclopropanol synthesis, the interaction of esters with 2:1 or 3:1 mixtures of alkyl Grignard reagents and Ti(OiPr)4 at low temperatures, has been conducted, in order to ascertain which reactive intermediates are involved and how they are interconverted. Because of the nature of the ultimate product, one of the most obvious intermediates is the 1,1-diisopropoxy-1-titanacyclopropane stemming from the epititanation of the alkene set free from the alkyl Grignard reagent employed. A search for the formation of such a titanocycle by warming an ethereal solution of either Et2Ti(OiPr)2 or iPr 2Ti(OiPr)2 between -78 °C and +25 °C was attempted by chemical trapping with either an ester or nitrile. In this manner it was shown that such a titanocycle was formed in the case of Et2Ti(OiPr) 2 but not with iPr2Ti(OiPr)2. As to the role of two other potential intermediates, Ti(OiPr)2 and R 2Ti(OiPr)2, it was demonstrated that preformed Ti(OiPr)2 in the presence of ethylene and an ester does not form the corresponding cyclopropanol. Thus, under the reaction conditions Ti(OiPr) 2 cannot perform the direct epimetallation necessary to produce the requisite titanacyclopropane. On the other hand, either iPr 2Ti(OiPr)2 or Et2-Ti(OiPr)2 can achieve the transfer-epititanation of ethylene at low temperatures and hence with methyl benzoate yield 1-phenyl-1-cyclopropanol. In contrast, neither iPr2Ti(OiPr)2 nor Et2Ti(OiPr) 2 can at low temperatures transfer-epititanate propylene. This difference in alkene reactivity can be ascribed to steric factors operating in the proposed octahedral transition state for transfer-epimetallation. Finally, by introducing free ethylene into such Kulinkovich reaction mixtures, either by ethylene gas itself or a third equivalent of EtMgX, the isolated yields of cyclopropanols were more than doubled over those obtained with a 1:2 ratio of Ti(OiPr)4/EtMgX. From this observation one can conclude that free ethylene catalytically initiates the Kulinkovich reaction by coordinating with Et2Ti(OiPr)2 and undergoes transfer-epititanation to produce the requisite titanacyclopropane and thereby liberates ethylene, which perpetuates the reaction. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Reactions of Carbonyl Compounds with Benzyl Chloromethyl Ether of Diiodomethane in the Presence of Samarium(II) Iodide or Metallic Samarium. New Routes to 1,2-Diols, Iodohydrins and Cyclopropanols

Carbonyl compounds react with benzyl chloromethyl ether in the presence of samarium(II) iodide to afford the corresponding addition products which, when subsequently hydrogenolysed, yield 1,2-diols.Simple aldehydes and ketones react with diiodomethane in the presence of samarium metal to give iodohydrins in good yields.Under similar reaction conditions, α-halogeno substituted ketones and aromatic 1,4-diketones are converted into cyclopropanols.These cyclopropanations have been shown to rpoceed through the initial generation of samarium enolates, followed by the Simmons-Smith type reaction.A novel transformation of esters to cyclopropanols via tandem one-carbon homologation is also described.

DIVALENT SAMARIUM-INDUCED CYCLOPROPANATION OF LITHIUM ENOLATES. A ONE-POT SYNTHESIS OF CYCLOPROPANOLS FROM KETONES

Lithium enolates, generated by deprotonation of ketones with lithium diisopropylamide, react with diiodomethane in the presence of SmI2 to give cyclopropanols.