124154-59-2

Usage

Usage

Used in the synthesis of fragrances and flavors, found in perfumes, soaps, and cosmetics, intermediate in pharmaceutical and agrochemical production

Physical properties

White solid at room temperature, slightly soluble in water

Chemical properties

Used in illicit production of MDMA, subject to regulation and monitoring by government agencies

Upstream product

• 114067-34-4 (3-methyl-2-butenyl)trifluorosilane 
• 123-11-5 4-methoxy-benzaldehyde 
• 78-79-5 isoprene 
• 2186-92-7 p-Anisaldehyde dimethyl acetal 
• 870-63-3 prenyl bromide 
• 113365-21-2 1,1-diphenyl-2,2-dimethyl-3-buten-1-ol 
• 598-25-4 Dimethylallene 
• 105-13-5 4-Methoxybenzyl alcohol 
• 10276-04-7 3-methyl-1-phenylsulfanylbut-2-ene 

Relevant academic research and scientific papers

Tetrakis(dimethylamino)ethylene (TDAE) as a potent electron source for Cr-mediated allylation of aldehydes and ketones

A new combination of organic reductant, tetrakis(dimethylamino)ethylene, and transition metal catalysts is reported for allylation of aldehydes and ketones.

Photocatalytic Umpolung Synthesis of Nucleophilic π-Allylcobalt Complexes for Allylation of Aldehydes

The concept of "umpolung"reactivity of π-allylmetal complexes has been developed as a powerful method for the allylation of aldehydes. This paper describes the photocatalytic umpolung strategy for the synthesis of nucleophilic allylcobalt complexes through a single-electron-transfer (SET) process. This strategy enables the metallaphotoredox allylation of carbonyls with allyl acetate using organic N,N-diisopropylethylamine as the terminal reductant bypassing the use of a stoichiometric amount of metals. Ultraviolet-visible spectroscopy was used to monitor the redox changes of cobalt in the reaction.

Ruthenium-catalyzed C-C bond forming transfer hydrogenation: Carbonyl allylation from the alcohol or aldehyde oxidation level employing acyclic 1,3-dienes as surrogates to preformed allyl metal reagents

Under the conditions of ruthenium-catalyzed transfer hydrogenation, commercially available acyclic 1,3-dienes, butadiene, isoprene, and 2,3-dimethylbutadiene, couple to benzylic alcohols 1a-6a to furnish products of carbonyl crotylation 1b-6b, carbonyl isoprenylation 1c-6c, and carbonyl reverse 2-methyl prenylation 1d-6d. Under related transfer hydrogenation conditions employing isopropanol as terminal reductant, isoprene couples to aldehydes 7a-9a to furnish identical products of carbonyl isoprenylation 1c-3c. Thus, carbonyl allylation is achieved from the alcohol or the aldehyde oxidation level in the absence of preformed allyl metal reagents. Coupling to aliphatic alcohols (isoprene to 1-nonanol, 65% isolated yield) and allylic alcohols (isoprene to geraniol, 75% isolated yield) also is demonstrated. Isotopic labeling studies corroborate a mechanism involving hydrogen donation from the reactant alcohol or sacrificial alcohol (i-PrOH). Copyright

Catalytic C-C coupling via transfer hydrogenation: Reverse prenylation, crotylation, and allylation from the alcohol or aldehyde oxidation level

We report byproduct-free carbonyl reverse prenylation, crotylation, and allylation from the alcohol oxidation state via alcohol-allene hydrogen autotransfer. Specifically, exposure of alcohols 1a-6a to 1,1-dimethylallene, methylallene, and allene in the presence of [Ir(cod)(BIPHEP)]BARF (5-7.5 mol %) delivers reverse prenylation products 1c-6c, crotylation products 1d-3d, and allylation product 1e. Similarly, under the conditions of transfer hydrogenation employing isopropanol as terminal reductant, aldehydes 1b-6b are converted to the very same adducts 1c-6c, 1d-3d, and 1e. Isotopic labeling studies corroborate a mechanism involving hydrogen donation from the reactant alcohol or sacrificial alcohol (i-PrOH). The ability to achieve carbonyl addition directly from the alcohol oxidation level circumvents the redox manipulations so often required to convert alcohols to aldehydes. Further, through hydrogen autotransfer, there resides the potential to develop myriad byproduct-free carbonyl additions wherein alcohols and π-unsaturated compounds are exploited as coupling partners. Copyright

Dibutyltin oxide catalyzed allyl-transfer reaction from tertiary homoallylic alcohols to aldehydes

A catalytic allyl-transfer reaction from tertiary homoallylic alcohols to aldehydes was achieved using dibutyltin oxide as a catalyst in toluene under reflux conditions. Various secondary homoallylic alcohols were prepared in high yield (up to 99%). When β-alkylated tertiary homoallylic alcohols were used, branched products were exclusively obtained. Georg Thieme Verlag Stuttgart.

In situ formation of allyl ketones via Hiyama-Nozaki reactions followed by a chromium-mediated Oppenauer oxidation

In Hiyama-Nozaki reactions of allylchromium with aldehydes the expected products are homo-allylalcohols. However, oxidation products derived from these, predominantly allyl ketones, can be common side products. This can be explained by an Oppenauer-(Meerwein-Ponndorf-Verley)-type mechanism (OMPV-reaction). The amount of oxidation is strongly dependent on the substitution pattern of the reaction partners and the reaction conditions. An appropriate choice of these can lead to preferential formation of ketones instead of the alcohols. In addition to its synthetic usefulness, the oxidation-reduction equilibrium is of the utmost importance for the design of enantioselective Hiyama-Nozaki reactions because it is also a potential racemization pathway.

Indium mediated allylation and propargylation reactions of dimethyl acetals and ketals

Indium mediated allylation and propargylation reactions of acetals and ketals with various allyl or propargyl bromides in aqueous media successfully provided the corresponding homoallylic or homopropargylic (and allenylic) alcohol, respectively, in moderate to good yields. Highly chemoselective allylation is also described. The ketal and aryl acetal could be selectively allylated over the aliphatic one in 80-84% yields.

A highly atom efficient, solvent promoted addition of tetraallylic, tetraallenic, and tetrapropargylic stannanes to carbonyl compounds

Tetraallylic, tetraallenic, and tetrapropargylic stannanes (0.25 equiv) react with aldehydes in methanol to provide unsaturated alcohols in good to excellent yields (56-99%). These reactions proceed exclusively with allylic rearrangement for tetra(2-butenyl)tin 2b and tetra(1,2-butadienyl)-tin 16c and predominantly with allylic rearrangement for tetrapropadienyltin 16a and tetra(2-butynyl)tin 6e. Allylation reactions also proceeded smoothly with reactive ketones such as ethyl pyruvate (9a) and cyclohexanone (9b). The corresponding TFA-catalyzed reactions of dimethyl acetals 4d and 4e are regiospecific with allylic rearrangement.

Reaction of allylmanganese(II) reagents with aldehydes

The reaction of allylmanganese(II) reagents with aldehydes gives alcohols with high regioselectivity. The allylmanganese(II) reagents are prepared by transmetallation between manganese(II) chloride and allyllithium compounds which are generated from allyl

Palladium-catalysed Carbonyl Allylation by Isoprene via Regioselective 1,4-Addition of Tin Hydride formed in situ

Isoprene reacts with aldehydes in the presence of a catalytic amount of Pd(OAc)2-4PPh3 or Pd(PPh3)4 and a stoichiometric amount of SnCl2 at 40-50 deg C in AcOH-H2O to produce 1-substituted 2,2-dimethyl-3-buten-1-ols regioselectively.