38691-01-9

Upstream product

• 1444-65-1 (RS)-2-phenylcyclohexanone 
• 541-41-3 chloroformic acid ethyl ester 
• 1483-72-3 diphenyliodonium chloride 
• 1655-07-8 ethyl 2-oxocyclohexane carboxylate 
• 3049-07-8 pentaphenylbismuth 
• 3076-54-8 phenyllead(IV) triacetate 
• 14190-17-1 diphenyliodonium acetate 
• 83566-42-1 tetraphenylbismuth acetate 
• 83566-45-4 tetraphenylbismuth trifluoromethanesulphonate 
• 83566-43-2 tetraphenyl-bismuth trifluoroacetate 
• 83566-44-3 tetraphenylbismuth 4-methylbenzenesulfonate 
• 214534-44-8 diphenyliodonium (1S)-camphor-10-sulfonate 
• 6280-87-1 δ-chlorovaleronitrile 
• 1403893-43-5 C₁₀H₁₁BrO₂Zn 

Downstream Products

• 55285-94-4 1-Phenyl-2-thioxo-cyclohexanecarboxylic acid ethyl ester 
• 55285-88-6 2-Mercapto-1-phenyl-cyclohex-2-enecarboxylic acid ethyl ester 

Relevant academic research and scientific papers

Arynes and Cyclic Alkynes as Synthetic Building Blocks for Stereodefined Quaternary Centers

We report a facile method to synthesize stereodefined quaternary centers from reactions of arynes and related strained intermediates using β-ketoester-derived substrates. The conversion of β-ketoesters to chiral enamines is followed by reaction with in situ generated strained arynes or cyclic alkynes. Hydrolytic workup provides the arylated or alkenylated products in enantiomeric excesses as high as 96%. We also describe the one-pot conversion of a β-ketoester substrate to the corresponding enantioenriched α-arylated product. Computations show how chirality is transferred from the N-bound chiral auxiliary to the final products. These are the first theoretical studies of aryne trapping by chiral nucleophiles to set new stereocenters. Our approach provides a solution to the challenging problem of stereoselective β-ketoester arylation/alkenylation, with formation of a quaternary center.

Electrochemical-Induced Ring Transformation of Cyclic α-(ortho-Iodophenyl)-β-oxoesters

Cyclic α-(ortho-iodophenyl)-β-oxoesters were converted in a ring-expanding transformation to furnish benzannulated cycloalkanone carboxylic esters. The reaction sequence started by electrochemical reduction of the iodoarene moiety. In a mechanistic rationale, the resulting carbanionic species was adding to the carbonyl group under formation of a strained, tricyclic benzocyclobutene intermediate, which underwent carbon–carbon bond cleavage and rearrangement of the carbon skeleton by retro-aldol reaction. The scope of the reaction sequence was investigated by converting cyclic oxoesters with different ring sizes yielding benzocycloheptanone, -nonanone and -decanone derivatives in moderate to good yields. Furthermore, acyclic starting materials and cyclic compounds carrying additional substituents on the iodophenyl ring were submitted to this reaction sequence. The starting materials for this transformation are straightforwardly obtained by conversion of β-oxoesters with phenyliodobis(trifluoroacetate).

Tandem one-pot construction of indoles via palladium and copper-catalyzed coupling reactions of the blaise reaction intermediate

The palladium-catalyzed intramolecular N-arylation of the Blaise reaction intermediate, formed by reaction of nitriles with an in situ generated Reformatsky reagent from ethyl -bromo - (2-bromophenyl)acetate and zinc, afforded indoles in good yields. Exte

Chemoselective intramolecular alkylation of the Blaise reaction intermediates: Tandem one-pot synthesis of exo -cyclic enaminoesters and their applications toward the synthesis of N -heterocyclic compounds

The intramolecular alkylative reactivity and N/C selectivity of the various Blaise reaction intermediates, which are formed from the reaction of the Reformatsky reagents with ω-chloroalkyl nitriles, did not reach the synthetic potential as an entry to exo-cyclic enaminoesters. To circumvent this issue, various additives were investigated, among which the addition of NaHMDS dramatically enhanced the reactivity and N/C selectivity. This modification provided a highly efficient route for the synthesis of various N-fused heterocyclic compounds, as it requires only two steps from nitriles.

Sulfoxide-mediated α-arylation of carbonyl compounds

A novel sulfoxide-mediated α-arylation of carbonyl compounds is reported. This reaction proceeds under very mild conditions at room temperature and does not require any transition-metal promoter or catalyst.

α-Arylation by rearrangement: On the reaction of enolates with diaryliodonium salts

Surprising equilibration: A new mechanism for the title reaction is supported by DFT calculations and experimental observations. The C-I and OI intermediates are isoenergetic and equilibrate quickly. Thus, any chiral information induced in the initial complex will be destroyed. In the final CC bond-forming step, a [2,3]-rearrangement from the O-I bonded intermediate is slightly preferred over the [1,2]elimination from the C-I bonded isomer (see scheme). (Figure Presented)

A new, efficient method for direct α-alkenylation of β-dicarbonyl compounds and phenols using alkenyltriarylbismuthonium salts

Direct α-alkenylation of β-keto esters, β-diketone, and phenols with alkenyltriarylbismuthonium salts proceeded smoothly in the presence of 1,1,3,3-tetramethylguanidine to afford the corresponding α-alkenylated carbonyl compounds (β,γ-unsaturated carbonyl compounds) in good yields. The high leaving ability of the triarylbismuthonio group is a key driving force to achieve the C-C bond formation at the vinylic carbon under mild conditions.

Synthesis and reactivity of chiral pentavalent bismuth derivatives

Eight new pentavalent organobismuth derivatives were synthesized by the reactions of triphenylbismuth or phenyl-2,2"-biphenylenebismuth with chiral (1R)-(-)-camphor-10-sulfonic, (-)-menthyloxyacetic, or (R)-3-phenylbutyric acids. Enantioselective C-arylat

Synthesis and reactivity of pentavalent biphenyl-2,2′-ylenebismuth derivatives

Phenylbiphenyl-2,2′-ylenebismuth diacetate reacted with nucleophiles under basic conditions to give modest to good yields of the C-phenylated substrates. Under copper catalysis, it reacted with hydroxy or amino groups to give the products of O- or N-phenylation. In both sets of reaction conditions, this reagent showed a reduced reactivity compared to the analogous triphenylbismuth diacetate reagent. It showed also a high regioselectivity as only the phenyl derivatives were detected and isolated. The Royal Society of Chemistry 2000.

The Chemistry of Pentavalent Organobismuth Reagents. Part 7. The Possible Role of Radical Mechanisms in the Phenylation Process for Bismuth(V), and Related Lead(IV), Iodine(III), and Antimony(V) Reagents

The phenylation reactions of bismuth(V), lead(IV), and iodine(III) have been examined to test the presence or absence of phenyl radicals.In the case of several bismuth(V) reactions the presence of phenyl radicals has been detected, but it has been shown, by use of a large excess of radical trapping agent, that these radicals have nothing to do with the phenylation process.In the same way, the other phenylation reactions fail to respond to a large excess of a radical trap.