17202-32-3

Upstream product

• 89641-49-6 1,2,3-Tribrom-cyclohexan 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 144773-93-3 1,5-dibromocyclopentene 
• 2568-36-7 6,6-dibromobicylo[3.1.0]hexane 
• 75-25-2 Bromoform 
• 142-29-0 cyclopentene 

Downstream Products

• 3727-48-8 2-bromocyclohexa-1,3-diene 
• 3727-47-7 1-bromocyclohexa-1,3-diene 
• 152510-75-3 (2-Bromo-cyclohex-2-enyl)-dimethyl-phenyl-silane 
• 118451-61-9 (2-bromo-cyclohex-2-enyl)-trimethyl-silane 
• 4736-37-2 2-Brom-3-<2-hydroxy-ethoxy>-cyclohexen 
• 161196-41-4 3-azido-2-bromocyclohexene 
• 182322-35-6 diethyl 2-(2-bromocyclohex-2-enyl)malonate 
• 364061-67-6 N-(2-Bromoallyl)-N-(2-bromo-2-cyclohexenyl)-4-methylaniline 
• 475040-19-8 N-(2-bromo-2-cyclohexenyl)-2-fluoro-N-methylaniline 
• 591727-27-4 tert-butyl (2-bromocyclohex-2-enyl)acetate 
• 913818-50-5 6-(2-acetylphenoxy)-1-bromocyclohexene 
• 907218-81-9 2-bromo-N-(furan-2-ylmethyl)cyclohex-2-en-1-amine 
• 1005214-45-8 2-bromo-N-((5-methylfuran-2-yl)methyl)cyclohex-2-en-1-amine 

Relevant academic research and scientific papers

Divergent Synthesis of Bioactive Dithiodiketopiperazine Natural Products Based on a Double C(sp3)?H Activation Strategy

This article provides a detailed report of our efforts to synthesize the dithiodiketopiperazine (DTP) natural products (?)-epicoccin G and (?)-rostratin A using a double C(sp3)?H activation strategy. The strategy's viability was first established on a model system lacking the C8/C8’ alcohols. Then, an efficient stereoselective route including an organocatalytic epoxidation was secured to access a key bis-triflate substrate. This bis-triflate served as the functional handles for the key transformation of the synthesis: a double C(sp3)?H activation. The successful double activation opened access to a common intermediate for both natural products in high overall yield and on a multigram scale. After several unsuccessful attempts, this intermediate was efficiently converted to (?)-epicoccin G and to the more challenging (?)-rostratin A via suitable oxidation/reduction and protecting group sequences, and via a final sulfuration that occurred in good yield and high diastereoselectivity. These efforts culminated in the synthesis of (?)-epicoccin G and (?)-rostratin A in high overall yields (19.6 % over 14 steps and 12.7 % over 17 steps, respectively), with the latter being obtained on a 500 mg scale. Toxicity assessments of these natural products and several analogues (including the newly synthesized epicoccin K) in the leukemia cell line K562 confirmed the importance of the disulfide bridge for activity and identified dianhydrorostratin A as a 20x more potent analogue.

Simple and efficient synthesis of bromine-substituted 1,3-dienes and 1,3,5-cycloheptatriene by vacuum pyrolysis of gem-dibromocyclopropanes

To establish whether the results obtained by the gas phase pyrolysis of 6,6-dihalobicyclo[3.1.0]hexanes by HeI photoelectron spectroscopy using a high power CW CO2 laser as a directed heat source can be achieved on a preparatory scale using a modified apparatus, we carried out the gas phase pyrolysis of a few representative gem-dibromocyclopropanes such as 1,1-dibromo-2,2,3,3-tetramethylcyclopropane (1), 1,1-dibromo-2,2-dimethyl-cyclopropane (2), 1,1-dibromo-cis-2,3-dimethylcyclopropane (3), 1,1-dibromo-trans-2,3-dimethylcyclopropane (4), 6,6-dibromobicyclo[3.1.0]hexane (5) and 7,7-dibromobicyclo[4.1.0]heptane (6). Except 7,7-dibromobicyclo[4.1.0]heptane, that gave 1,3,5-cycloheptatriene in 72% yield at 525°C, 1, 2, 3, 4 and 5 readily lose HBr at 400-560°C in the gas phase to produce β-bromo-1,3-dienes in high chemical yields and purity. The dienes are potentially useful starting substrates for the Diels-Alder reactions.

SilverCatalyzed Cascade Carboxylation and Cyclization of Trimethyl(2-methylenebut-3-yn-1-yl)silane Derivatives

C-C bond-forming carboxylation and cyclization of trimethyl(2-methylenebut-3-yn-1-yl)silane derivatives and carbon dioxide was developed. Silver catalysts and CsF promoted the reaction to afford the corresponding 2-furanone and 2-pyrone derivatives in goo

Synthesis of hexahydroindoles by intramolecular C sp 3-H alkenylation: Application to the synthesis of the core of aeruginosins

Give me five: Pd-catalyzed intramolecular C sp 3-H arylations have been successfully extended to alkenylations. This method shows remarkable selectivity and gives synthetically useful hexahydroindoles, as illustrated with the synthesis of the octahydroind

Copper-catalyzed asymmetric allylic alkylation of racemic cyclic substrates: Application of dynamic kinetic asymmetric transformation (DYKAT)

The copper-catalyzed asymmetric allylic alkylation (AAA) is of great interest in organic synthesis. This reaction was extensively studied using a broad range of substrates, ligands and organometallic reagents. However, the use of racemic substrates was still limited. Although some processes of kinetic resolution are reported in the literature, no examples of quantitative deracemization are described as is the case for the Pd-catalyzed allylic alkylation. We present here a full account of our investigations through the development of the first example of such a process in copper-catalyzed AAA. High enantioselectivities (up to 99% ee), scope of the reaction and mechanistic considerations are reported herein.

Catalytic formal homo-Nazarov cyclization

The first catalytic method for the cyclization of vinyl-cyclopropyl ketones (formal homo-Nazarov reaction) is reported. Starting from activated cyclopropanes, heterocyclic, and carbocyclic compounds were obtained under mild conditions using Bronsted acid catalysts. Preliminary investigation of the reaction mechanism indicated a stepwise process.

Thermal intramolecular Diels-Alder reaction of furan; synthesis of nitrogen tetracycles, isobenzofuran and isobenzothiophene

Thermal intramolecular Diels-Alder (IMDA) reaction of furan cored compounds has been further investigated; a series of key precursors to the IMDA reaction of furan diene (9a-c) have been prepared via facile alkylation and protection. While the cycloadditi

2-Halo-2-cyclohexenols from 6,6-dihalobicyclo-[3.1.0]hexanes and dimethyl sulfoxide. Studies towards a non-basic hydroxide equivalent

A practical, high yielding, cheap and mild method for the synthesis of 2-halo-2-cycloalkenols, especially 2-bromo-2-cyclohexenol, is reported. Direct conversion from a variety of thermally labile n,n-dihalobicyclo[n-3.1.0]alkanes to 2-halo-2-cycloalkenols can be achieved without using silver salts by simple heating in DMSO. The intermediate 1,n-dihalocycloalkenes immediately undergo indirect allylic substitution with DMSO to yield the corresponding halocycloalkenols. A possible mechanism for the substitution step comprises nucleophilic attack by DMSO followed by a Pummerer rearrangement and hydrolytic decomposition. Kinetic and mechanistic experiments to verify the course of the reaction are presented. Acta Chemica Scandinavica 1997.

An Attempted Synthesis of 1,2-Cyclopentadiene and Wurtz-Like Condensation Products in the Reaction of 1,2-Dibromocycloalkenes

Fluoride ion-promoted elimination of 2-bromo-3-trimethylsilyl cyclohexene 16 and 2-bromo-3-trimethylsilyl cycloheptene 17 has been successfully used for synthesis of strained six- and seven- membered cyclic allenes.When 2-bromo-3-trimethylsilyl cyclopentene 5 was submitted to fluoride ion-promoted elimination only Wurtz-like dimeric products 6 and 7 were obtained instead of the expected 1,2-cyclopentadiene 8.Interestingly, reaction of 2,3-dibromocyclopentene 4, 2,3-dibromocyclohexene 12, and 2,3-dibromocycloheptene 13 with zinc gave only Wurtz-like dimeric products, (6,7), (18,19) and (20,21), respectively.

Convergent Routes to the Dioxolophenanthridin-6(5H)-one and 2,3,4,4a-Tetrahydrodioxolophenanthridin-6(5H)-one Nuclei. Application to Syntheses of the Amaryllidaceae Alkaloids Crinasiadine, N-Methylcrinasiadine and Trisphaeridine

Convergent routes to the title nuclei, (1) and (6), have been developed.Thus, Suzuki coupling of boronic acid (8) with aryl bromide (9) gave the biarylylcarbamate (7) which, on treatment with phosphorus oxychloride (POCl3), underwent Bischler-Napieralski