3756-30-7

Usage

Uses

Used in Pharmaceutical Industry:
Methallyl iodide is used as a reactant for the preparation of chroman-substituted, tetrahydroquinoline-substituted, and thiochroman-substituted ureas and thioureas. These compounds have potential applications as anticancer agents, making methallyl iodide an important component in the development of new cancer treatments.

Upstream product

• 563-47-3 3-Chloro-2-methylpropene 
• 142820-20-0 2-methylallyl methanesulfonate 

Downstream Products

• 76403-21-9 (±)-4-methyl-2-phenyl-4-pentenoic acid 
• 151813-41-1 2-(2-Methylpropenyl)-2-p-methoxyphenylacetic acid 
• 91671-16-8 2,6-dimethyl-4-(α-styryl)-1,6-heptadien-4-ol 
• 99706-84-0 2-butyl-2-(2-methylprop-2-en-1-yl)-3-<(E)-methoxy(phenylthio)methylene>cyclohexan-1-one 
• 134818-39-6 2-(1-cyclohexenyl)-2-(2-methyl-2-propenyl)-1,3-dithiane 
• 99706-85-1 2-<(tert-butoxycarbonyl)methyl>-2-(2-methylprop-2-en-1-yl)-3-<(E)-methoxy(phenylthio)methylene>cyclohexan-1-one 
• 91671-28-2 2-(4-iodophenyl)-4-methyl-4-penten-2-ol 
• 112654-30-5 4,4-dicyano-2,7-dimethyl-5-phenylocta-1,7-diene 
• 81925-76-0 2,6-Dimethyl-4-phenyl-1,6-heptadien-4-ol 
• 91671-17-9 2,6-dimethyl-4-(α-phenethyl)-1,6-heptadien-4-ol 
• 91671-18-0 methyl 2-<4-(1-hydroxy-1,3-dimethyl-3-butenyl)phenyl>-propionate 
• 101566-44-3 2-p-tolyl-4-methyl-4-pentanoic acid 
• 151813-47-7 methyl 2-(2-methyl-2-propenyl)-4-phenylbutanoate 
• 91671-30-6 2-(4-acetoxy-3-methoxyphenyl)-4-methyl-4-penten-2-ol 

Relevant academic research and scientific papers

Dynamic Kinetic Resolution of Aldehydes by Hydroacylation

We report a dynamic kinetic resolution (DKR) of chiral 4-pentenals by olefin hydroacylation. A primary amine racemizes the aldehyde substrate via enamine formation and hydrolysis. Then, a cationic rhodium catalyst promotes hydroacylation to generate α,γ-disubstituted cyclopentanones with high enantio- and diastereoselectivities.

Evolution of a total synthesis of (-)-kendomycin exploiting a Petasis-Ferrier rearrangement/ring-closing olefin metathesis strategy

A convergent stereocontrolled total synthesis of (-)-kendomycin (1) has been achieved. The synthesis proceeds with a longest linear sequence of 21 steps, beginning with commercially available 2,4-dimethoxy-3-methylbenzaldehyde (12). Highlights of the synthesis include an effective Petasis-Ferrier union/rearrangement tactic to construct the sterically encumbered tetrahydropyran ring, a ring-closing metathesis to generate the C(4a-13-20a) macrocycle, an effective epoxidation/deoxygenation sequence to isomerize the C(13,14) olefin, and a biomimetic quinone-methide-lactol assembly to complete the synthesis.

Fe/Cr- and Co/Cr-mediated catalytic asymmetric 2-haloallylations of aldehydes

The first example to couple aldehydes and 3-bromo-2-halopropenes in a catalytic asymmetric manner is reported. The coupling reaction is effected by the use of a chiral sulfonamide-Cr complex (prepared in situ from 1d, CrBr3, Fe(III) or from Co(II), Et3N, and Mn), TMSCl, and 2,6-lutidine. The method reported here is operationally simple and scalable, furnishing 3-halohomoallylic alcohols with a synthetically useful level of enantiomeric excess. Copyright

Diastereoselective synthesis of substituted tetrahydroquinoline-4-carboxylic esters by a tandem reduction-reductive amination reaction

A diastereoselective synthesis of 1-methyl-2-alkyl- and 2-alkyl-1,2,3,4-tetrahydroquinoline-4-carboxylic esters has been developed from methyl (2-nitrophenyl)acetate (1). The method involves alkylation of 1 with an allylic halide, ozonolysis of the double bond, and catalytic hydrogenation. The final hydrogenation initiates a tandem sequence involving (1) reduction of the aromatic nitro group, (2) condensation of the aniline or hydroxylamine8 nitrogen with the side chain carbonyl, (3) reduction of the resulting nitrogen intermediate, and (4) reductive amination of the tetrahydroquinoline with formaldehyde produced in the ozonolysis to give a methyl (±)-1-methyl-2-alkyl-1,2,3,4-tetrahydroquinoline-4-carboxylate. Removal of the formaldehyde prior to hydrogenation gives the simple (±)-2-alkyl derivatives. The products are isolated in high yield as single diastereomers having the C-2 alkyl group cis to the C-4 carboxylic ester. The reaction has been extended to the synthesis of tricyclic structures with similar high diastereoselection.

Organoaluminum-Promoted Cyclization of Olefinic Epoxides. a New and Stereoselective Approach to Cyclohexane Frameworks

A new, general synthetic method of six-membered carbocycles has been demonstrated, which involves the stereo-controlled cyclization of olefinic epoxides with methylaluminum bis(4-bromo-2,6-di-t-butylphenoxide) (MABR) via the epoxide rearrangement and subsequent intramolecular ene reaction with high stereoselectivity. This strategy is shown to be highly useful in the stereoselective synthesis of the basic skeleton of various terpenes.

Asymmetric catalysis. Asymmetric catalytic intramolecular hydroacylation of 4-pentenals using chiral rhodium diphosphine catalysts

Catalysts of the type [Rh(chiral diphosphine)]+ convert 4-substituted 4-pentenals into the corresponding 3-substituted cyclopentanones with generally high turnover numbers and frequencies at 25 °C. The enantioselectivities of various substituted 4-pentenals with two chiral diphosphines have been explored. It was found that with the binap catalyst, almost complete enantioselectivity is observed for 4-pentenal substrates bearing 4-substituted tertiary substituents and for ester groups. Ketonic substituents give very high enantioselectivities. The mechanism of intramolecular hydroacylation has been explored, and it is suggested that an important consideration for obtaining high turnover frequencies is related to the acyl-alkyl reductive elimination mechanism which is inferred to occur by a process similar to ester hydrolysis. The origin of the enantioselection is discussed in terms of the interactions between the phenyl groups of the phosphine and the substituent of the pentenal.

Unprecedented stereochemical control in the intramolecular ene-reactions of δ,ε-unsaturated aldehydes using exceptionally bulky organoaluminum reagents: Elucidation of the transition state

Unprecendented stereochemical control has been achieved in the type II intramolecular ene reactions of δ,ε-unsaturated aldehydes leading to trans-cyclohexanols with excellent selectivity under very mild conditions, using exceptionally bulky methylaluminum bis(4-bromo-2,6-di-tert-butylphenoxide) (MABR). Success of the stereocontrolled cyclization can be ascribable to the ability of this modified organoaluminum reagents, MABR, to change the conformation of the transition state. Examining the ene reactions of substrates 7, 11, 14 with MABR, the stereochemical outcome of the present organoaluminum-promoted intramolecular ene reactions is further elucidated.

RULES FOR RING CLOSURE: APPLICATION TO INTRAMOLECULAR ALDOL CONDENSATIONS IN POLYKETONIC SUBSTRATES

An extension of the nomenclature for classifying ring closures to include intramolecular reactions of enolate anions is described, and the rules governing such cyclizations are enumerated.The syntheses of the polyketonic substrates 4-acetyl-2,6-heptanedione (11), 4-acetyl-4-methyl-2,7-octanedione (24), and 3-acetyl-3-methyl-1,6-diphenyl-1,6-heptanedione (33) were carried out, and their base-induced intramolecular aldol condensations studied.With each substrate a favored 6-(enolendo)-exo-trig cyclization to produce cyclohexenone products was the only ring forming reaction observed, this process predominating in all instances over competing disfavored 5-(enolendo)exo-trig closures, and also over other competing favored cyclizations.The identity of the cyclization product 12 derived from 11 was confirmed by aromatizing 12 to 17, and alternately synthesizing 17 from 3-bromo-5-methylphenol.