67714-28-7

Upstream product

• 100-39-0 benzyl bromide 
• 1655-07-8 ethyl 2-oxocyclohexane carboxylate 
• 100-44-7 benzyl chloride 
• 138536-50-2 ethyl 1-(2-iodobenzyl)-2-oxocyclopentane-1-carboxylate 
• 2050-20-6 diethyl pimelate 
• 153851-18-4 ethyl 7-iodo-3-oxoheptanoate 

Downstream Products

• 858443-64-8 2-benzyl-heptanedioic acid 
• 936836-55-4 (1-benzyl-2-oxocyclohexyl)methyl diethoxyphosphinylacetate 
• 936836-56-5 8a-benzyl-5,6,7,7a-tetrahydrocyclohexa[c]pyran-3(1H)-one 
• 862202-17-3 2-benzyl-2-hydroxymethylcyclohexanone 
• 936836-51-0 ethyl 1-benzyl-(2,2-ethylenedioxy)cyclohexanecarboxylate 

Relevant academic research and scientific papers

A General Method for High-Pressure-Promoted Postfunctionalization of Unclosed Cryptands: Potential Phase-Transfer Catalysts

We report a high-pressure approach to facile late-stage functionalization of unclosed cryptands (UCs) (11 examples, yield up to 99%). Direct comparison of classic and high-pressure conditions of the quaternization reaction in a sterically crowded intraannular position is investigated, and differences in the reactivity of tertiary amine substrates are discussed. Finally, we demonstrated the application of UCs as catalysts for synthetically important alkylation reactions under phase-transfer conditions.

N-Heterocyclic olefins as efficient phase-transfer catalysts for base-promoted alkylation reactions

N-Heterocyclic olefins (NHOs) have very recently emerged as efficient promoters for several chemical reactions due to their strong Br?nsted/Lewis basicities. Here we report the novel application of NHOs as efficient phase-transfer organocatalysts for synt

Construction of functionalized carbocycles having contiguous tertiary carbinol and all-carbon stereogenic centers

A highly stereoselective protocol is reported for customizing functionalized carbocyclic building blocks (β-hydroxy esters) and bicyclic lactones with a stereoarray that contains contiguous tertiary carbinol and all-carbon stereocenters. The efficient asymmetric induction and diastereofacial selective addition of allyl and propargyl indiums to hindered α,α-disubstituted cycloalkanones is presented. The stereochemistry of representative products was unequivocally established from single-crystal X-ray crystal structure analyses, and a plausible reaction pathway was proposed to support the high diastereofacial selectivity.

Studies on diastereoselective reduction of cyclic β-ketoesters with boron hydrides. Part 4: The reductive profile of functionalized cyclohexanone derivatives

Reduction of 2-allyl-2-carboalkoxycyclohexanones (3d-f), 2-propyl-2-carboethoxycyclohexanone (3g) and 2-benzyl-2- carboethoxycyclohexanone (3h) with boron hydrides in the presence and absence of several chelating agents were studied. Molecular modeling studies using semiempirical PM3 method were performed in order to find a suitable explanation of the diastereoselection of ketone carbonyl faces during the reductive process, which yielded trans-2-allyl-2-carboethoxycyclohexanol (6e) and cis-2-allyl-2-carboethoxycyclohexanol (7e) in good diastereomeric excess by using inexpensive sodium and tetrabutylammonium borohydrides.

Synthesis of substituted cyclopropanes from 1,3-diols through the corresponding cyclic sulfates

The reaction of different cyclic sulfates 2 (easily prepared from the corresponding 1,3-diols 1 following the Sharpless methodology) with an excess of lithium powder and a catalytic amount of DTBB (5 mol %) leads to the corresponding substituted cyclopropanes 3 through a γ-elimination process, the sulfate ion acting as leaving group.

Utilization of Me3SiSnBu3 in organic synthesis I. Generation of stannyl anion from Me3SiSnBu3 and R4NX

A metal free stannyl anion generated from Me3SiSBu3 and R4NX in DMF reacted with an aryl halide bearing carbonyl group to produce an aryl anion via the so-called halogen-metal exchange process, which reacted with a carbonyl group to afford a cyclized product in good yield.

Photoinduced Molecular Transformations. Part 144. One-Carbon Intercalation of γ- and δ-Lactones involving the β-Scission of Alkoxyl Radicals as the Key Step: Synthesis of δ- and ε-Lactones with α-Substituents

A new general method of a one-carbon intercalation of γ-lactones to δ-lactones and δ-lactones to ε-lactones in three steps involving a selective β-scission of the alkoxyl racicals as the key step is described.The reactions of γ- and δ-lactones with lithioalkyl acetate gave an equilibrium mixture of alkyl (2-hydroxytetrahydrofuran-2-yl)acetates and alkyl (2-hydroxytetrahydropyran-2-yl)acetates, as well as their ring-opened isomers in 62-95percent yields, respectively.The photolysis of the hypoiodites of these lactols in benzene containing mercury(II) oxide and iodine with Pyrex-filtered light resulted in a selective endocyclic β-scission of the corresponding alkoxyl radicals to give alkyl iodoalkyl propanedioates in 33-70percent yields.Treatment of the iodoalkyl propanedioates with tetraethylammonium bromide and sodium hydride gave alkyl 3,4,5,6-tetrahydro-2-oxo-2H-pyran-3-carboxylates or alkyl 2,3,4,5,5a,6,7,8,9,9a-decahydro-2-oxobenzoxepine-3-carboxylate in 61-81percent yields.On the other hand, succesive treatment of ω-iodoalkyl propanedioates with tetraethylammonium bromide-sodium hydride and then benzyl bromide gave a α-disubstituted δ-lactone, which gave a α-monosubstituted δ-lactone upon heating in trifluoroacetic acid under reflux.Cyclopentanone can similarly be transformed into 2-substituted cyclohexanone via a three-step procedure.

Surface-mediated Solid-phase Reaction. Part 2. Highly Selective Mono- and Di-C-alkylation of 1,3-Dicarbonyl Compounds on the Surface of Alumina

Highly selective mono- and di-C-alkylation of 1,3-dicarbonyl compounds with different, structurally varied alkyl halides has been achieved in high yields through a simple solvent-free reaction on the surface of alumina impregnated with sodium or potassium alkoxide.

Regioselective α-Alkylation of Extended Enolates Derived from Enamines of β-Keto Esters. Studies Relating to the Synthesis of 2-Substituted 2-Alkoxycarbonylcycloalkanones

Enamines 4a-c, 5a-c and 6 have been prepared (from the corresponding 5-, 6- and 7-ring cyclic β-keto esters) and converted into enolates of general structure 2.These extended enolates react with alkyl halides at the α-site exclusively and the resulting adducts, exemplified by 7, have been hydrolysed to the corresponding 2-substituted 2-alkoxycarbonylcycloalkanones.These results are discussed in the context of the regioselectivity that has been reported for related enolates which tend, depending on the structure, to show a preference for γ-selectivity in their reactions with electrophiles.The asymmetric variant of the alkylation sequence described has also been examined but only modest enantioselectivity (up to 33percent e.e.) has been attained by incorporation of (S)-2-methoxymethylpyrrolidine 25, via enamine 26.Further progress was blocked by problems encountered in the synthesis of the requisite enamines when the more hindered C2-symmetric amines, such as (2R,5R)-2,5-dimethylpyrrolidine 27, were used, thereby limiting the more general synthetic utility and scope of this extended enolates.

Reaction of Metal Free Bu3Sn- Generated from Bu3SnSiMe3-R4NX with an Aryl or Vinyl Halide

Metal free stannyl anion generated from Bu3SnSiMe3 and R4NX in DMF reacted with an aryl or vinyl halide to produce the aryl or vinyl anion via so-called halogen-metal exchange process, which reacted with internal carbonyl group to afford cyclized product in good yield. Key Words: Bu3NSnSiMe3, Bu3Sn(1-)*R4N(1+), Metal free stannyl anion, Cyclization, Aryl or Vinyl anion