30857-70-6

Upstream product

• 30930-83-7 hexanal cyclohexylimine 
• 100-44-7 benzyl chloride 
• 14371-10-9 (E)-3-phenylpropenal 
• 109-72-8 n-butyllithium 
• 100-39-0 benzyl bromide 
• 724775-68-2 tert-butyl(hex-1-en-1-yl)isopropylamine 
• 25226-98-6 trans-cinnamaldehyde diethylacetal 
• 591-50-4 iodobenzene 
• 925-54-2 2-methylhexanal 
• 108-86-1 bromobenzene 
• 1116651-53-6 (E)-1-(hex-1-enyl)-2,2,6-trimethylpiperidine 
• 1436-34-6 1,2-Epoxyhexane 
• 131079-13-5 (Z)-1-(dimethylphenylsilyl)-2-formyl-1-hexene 
• 16510-48-8 2-Benzylhexanal-diethyl-acetal 

Downstream Products

• 5668-19-9 acide 2-benzyl-hexanoique 

Relevant academic research and scientific papers

Catalytic C-H Arylation of Aliphatic Aldehydes Enabled by a Transient Ligand

The direct arylation of aliphatic aldehydes has been established via Pd-catalyzed sp3 C-H bond functionalization in the presence of 3-aminopropanoic acids as transient directing groups. The reaction showed excellent functional group compatibility and chemoselectivity in which a predominant preference for functionalizing unactivated β-C-H bonds of methyl groups over others was achieved. In addition, C-H bonds of unactivated secondary sp3 carbons can also be functionalized. The extreme popularity and importance of aliphatic aldehydes would result in broad applications of this novel method in organic chemistry and medicinal sciences.

Arylation of aldehyde homoenolates with aryl bromides

A mild palladium catalyzed coupling of reactive aldehyde homoenolates with aryl bromides is described. Aldehyde homoenolates are generated by ring opening of cyclopropanols via a C-C cleavage step. The coupling generates aldehyde products at room temperature in 59-93% yield.

Synthesis and C-alkylation of hindered aldehyde enamines

A new reactivity mode of hindered lithium amides with terminal epoxides is described whereby aldehyde enamines are produced via a previously unrecognized reaction pathway. Some of these aldehyde enamines display unprecedented C-alkylation reactivity toward unactivated primary and secondary alkyl halides. For comparison, the reactivity of aldehyde enamines synthesized via a traditional condensation method was examined. C-rather than N-alkylation was the dominant reaction pathway found with a range of electrophiles, making this route to α-alkylated aldehydes more synthetically useful than previously reported.

Asymmetric synthesis of α-alkylated aldehydes using terminal epoxide-derived chiral enamines

(Chemical Equation Presented) Effective discrimination: Efficient lithium amide-induced terminal epoxide-enamine transformation provides the first enamines capable of generating α-alkylated aldehydes with high asymmetric induction by intermolecular nucleophilic substitution (see scheme).

Enamines from terminal epoxides and hindered lithium amides

A new reactivity mode of lithium amides with epoxides leads to hindered enamines. The reaction of some of these enamines with unactivated primary and secondary alkyl halides is described, which expands the range of electrophiles that one can use in the synthesis of mono-alkylated aldehydes. Copyright

Fluoride-Promoted Rearrangement of Organo Silicon Compounds: A New Synthesis of 2-(Arylmethyl)aldehydes from 1-Alkynes

A new approach to 2-(arylmethyl)aldehydes 4 based upon a 1,2-anionotropic rearrangement of an aryl group is presented. The synthetic sequence begins with a silylformylation reaction of terminal acetylenes 5 with aryl and heteroaryl silanes 6, followed by treatment of the products (Z)-1 with TBAF. The optimization of the experimental conditions of the fluoride-promoted step is described, together with the synthetic potentialities of the process. A plausible mechanism of the rearrangement reaction is reported that suggests the addition of the fluoride ion to the arylsilicon moiety of β-silylalkenals (Z)-1 and the consequent migration of the aryl group to the adjacent carbon atom. Both aryl and heteroaryl substituents can rearrange without any loss of configuration. Bromofunctionalized substrates undergo an intramolecular reaction that affords exclusively carbacyclobenzyl aldehydes, further enhancing the high synthetic value of this method.

New synthesis of α-benzylaldehydes from 2-(dimethylphenylsilylmethylene)alkanals by fluoride promoted phenyl migration

α-Benzyl aldehydes are prepared from easily available β-silylalkenals and fluoride reagents, under mild experimental conditions; the reaction occurs instantaneously with almost quantitative yields. A plausible mechanism is suggested, which involves a 1,2-

An easy access to enantio-enriched α-substituted aldehydes by carbolithiation of β-phenyl or β-silyl-α,β-ethylenic aldehydes, protected with the monolithioamide of a chiral diamine

Lithium amide derived from N,N,N′-trimethyl-1,2-diphenylethanediamine converts cinnamaldehyde to a lithium alkoxyamide which undergoes a regio- and stereoselective carbolithiation upon addition of various organolithiums. Subsequent hydrolysis or trapping with MeI delivers α-mono-, or α,β-disubstituted 3-phenylpropanals with e.e.s of 76-96%. Extension to a silylated α-enal is possible.

Carbolithiation of an α-amino lithio alkoxide derived from cinnamaldehyde

Cinnamaldehyde adds alkyllithiums on the carbon carbon double bond regioselectively, after protection by the amide of N,N,N' trimethylethanediamine. The benzyllithium reagent thus obtained reacts with electrophiles diastereoselectively.