22715-57-7

Usage

Type of compound

Brominated derivative of tetramethylcyclopropane

Structure

Cycloalkane with four methyl groups attached to the cyclopropane ring

Presence of bromine atoms

High reactivity

Chirality

Chiral compound with a non-superimposable mirror image

Applications

Used in organic synthesis as a reagent to synthesize other organic compounds

Handling and storage

Requires careful handling and storage to prevent hazardous chemical reactions

Upstream product

• 563-79-1 2,3-Dimethyl-2-butene 
• 75-25-2 Bromoform 
• 74-95-3 1,1-dibromomethane 
• 135226-15-2 dibromocarbene 
• 115-11-7 isobutene 
• 558-13-4 carbon tetrabromide 
• 563-78-0 2,3-Dimethyl-1-butene 
• 110426-98-7 (4aR,8aS)-9,9-Dibromo-1,4-dihydro-4a,8a-methano-naphthalene 

Downstream Products

• 53081-83-7 2,2,3,3-Tetramethyl-4,4-diphenylcyclobutanon 
• 4773-87-9 3-bromo-2,4-dimethylpenta-1,3-diene 
• 3422-07-9 1-isopropenyl-1-methylcyclopropane 
• 56799-07-6 α-<2,2,3,3-Tetramethyl-1-(methylthio)-cyclopropyl>-benzylalkohol 
• 90660-91-6 2-(2-bromo-1,1,3-trimethyl-2-butenyl)furan 
• 53422-93-8 3-bromo-2,4-dimethyl-2-penten-4-ol 
• 100082-44-8 1-bromo-1-(phenylthio)-2,2,3,3-tetramethylcyclopropane 
• 1442555-62-5 C₁₆H₂₄O 

Relevant academic research and scientific papers

EXPERIMENTAL EVIDENCE FOR A CORRELATION BETWEEN ISOSELECTIVE AND ISOKINETIC TEMPERATURES

From isokinetic temperatures β (Figures I and II) and activation enthalpies (Table I) an isoselective temperature of 368 K is calculated for cycloaddition reactions of dihalocarbenes with alkenes.This is in excellent accord with the experimental value of 360 +/- 10 K.

A PHOTOCHEMICAL SOURCE OF DIBROMO- AND DICHLOROCARBENE A CAUTIONARY TALE REGARDING THE STEREOCHEMISTRY OF DIBROMOCARBENE ADDITION REACTIONS

Photolysis of triene 3a or 3b yields dibromo- and dichlorocarbene which can be transferred to olefins in good yield.A warning is offered regarding the data recently interpreted as being "only consistent" with the formation of an intermediate in the addition of dibromocarbene to trans-cyclooctene.

A stereospecific anionic reduction of gem-bromohalocyclopropanes by the dimsyl anion

The reaction of several 2,2,3,3-tetrasubstituted-gem-bromohalocyclopropanes with t-BuOK in DMSO unexpectedly yielded the monohalocyclopropanes in good yield.A closer investigation revealed that this reaction must be initiated by a nucleophilic attack by the dimsyl anion (CH3SOCH2(1-)) on bromine with subsequent protonation of the carbenoid intermediate.The reaction occurs rapidly (within 2 minutes) and is not inhibited by radical scavengers or in the dark.Only bromine, and not chlorine, is reduced, and the intermediate cyclopropyl anion is configurationally stable under the reaction conditions.

Part 1: Efficient strategies for the construction of variably substituted bicyclo[5.3.1]undecenones (AB taxane ring systems)

Strategies for the construction of cyclic molecules containing variably substituted bicyclo[5.3.1]undecenones (AB taxane ring systems) are described. These routes employ a multi-component coupling protocol that utilizes sequential magnesium-mediated carbometallation of propargyl alcohols and intramolecular Diels-Alder reactions (IMDA). The cycloaddition generates the key eight-membered taxane ring as a single diastereomer, induced by preferential Lewis acid (diethylaluminum chloride or boron trifluoride etherate) complexation with the cross-ring oxygens, Both the electronic nature of the dienophile and the neighbouring group non-bonded interactions contribute to the success of these cycloadditions.

Two-Phase Synthesis of Taxol

Taxol (a brand name for paclitaxel) is widely regarded as among the most famed natural isolates ever discovered, and has been the subject of innumerable studies in both basic and applied science. Its documented success as an anticancer agent, coupled with early concerns over supply, stimulated a furious worldwide effort from chemists to provide a solution for its preparation through total synthesis. Those pioneering studies proved the feasibility of retrosynthetically guided access to synthetic Taxol, albeit in minute quantities and with enormous effort. In practice, all medicinal chemistry efforts and eventual commercialization have relied upon natural (plant material) or biosynthetically derived (synthetic biology) supplies. Here we show how a complementary divergent synthetic approach that is holistically patterned off of biosynthetic machinery for terpene synthesis can be used to arrive at Taxol.

Route optimization and synthesis of taxadienone

Early process development toward the scalable production of taxadienone on a decagram scale is described. A continuous flow reactor was employed to safely run a potentially hazardous cyclopropane ring opening. The route featured two copper-mediated additions, a Diels-Alder reaction and a palladium-catalyzed Negishi coupling, to construct the final structure.

Zinc-mediated CH-activation of tetrahydrofuran under mild conditions for the regioselective addition to aryl-propiolates

The CH-activation of THF is realized in a zinc-mediated process using a dibromocyclopropane as a crucial additive. The highly regioselective addition to aryl-substituted propiolates as well as the regio- and stereoselective addition to diynes are described.

Total synthesis of taxane terpenes: Cyclase phase Dedicated to Professor Melanie S. Sanford on the occasion of her receipt of the Tetrahedron Young Investigator Award

A full account of synthetic efforts toward a lowly oxidized taxane framework is presented. A non-natural taxane, dubbed 'taxadienone', was synthesized as our first entry into the taxane family of diterpenes. The final synthetic sequence illustrates a seven-step, gram-scale, and enantioselective route to this tricyclic compound in 18% overall yield. This product was then modified further to give (+)-taxadiene, the lowest oxidized member of the taxane family of natural products.

α-fluoro-2,2,3,3-tetramethylcyclopropanecarboxamide, a novel potent anticonvulsant derivative of a cyclic analogue of valproic acid

2,2,3,3-Tetramethylcyclopropanecarboxylic acid (TMCA, 4) is a cyclic analogue of the antiepileptic drug (AED) valproic acid (VPA) (1). α-F, α-Cl, R-Br, and R-methyl derivatives of 4 and their amides were synthesized and tested in rodent models for anticonvulsant potency and AED-induced teratogenicity. In the anticonvulsant rat-maximal electroshock (MES) and subcutaneous metrazol (scMet) tests, α-Cl-TMCD (17) had ED 50 values of 97 and 27 mg/kg, respectively. α-F-TMCD (11) was 120 times more potent than VPA in the rat-scMet test (ED50) 6 mg/kg) and had a protective index (PI) TD50/ED50) of 20. In the 6 Hz psychomotor mouse model 11 had ED50 values of 57 mg/kg (32 mA) and 59 mg/kg (44 mA). The ED50 values of 11 in the hippocampal-kindled rat model and in the pilocarpine-induced-status rat model were 30 and 23 mg/kg, respectively. Unlike 1, 11 was nonteratogenic in mice. This novel compound has the potential to become a candidate for development as a new potent and safe antiepileptic and CNS drug.

Is a phase transfer catalyst really needed for gem-dihalocyclopropanation of alkenes with haloforms in the presence of alkali metal hydroxide?

Chloroform, bromoform and dibromochloromethane react with alkenes in the presence of cone. aq. sodium hydroxide, without phase-transfer catalyst, giving gem-dihalocyclopropanes. The process is particularly useful for preparation of gem-bromochlorocyclopropanes which are formed in good yields and in high selectivity.