330944-30-4

Upstream product

• 201230-82-2 carbon monoxide 
• 100-51-6 benzyl alcohol 
• 78-79-5 isoprene 
• 104-57-4 benzyl formate 
• 1373129-24-8 benzyl 4-methylpenta-2,3-dienote 
• 81867-37-0 benzyl iodoacetate 
• 3017-69-4 2-methyl-1-propenylbromide 
• 131401-46-2 (E)-4-methyl-pent-2-enoic acid benzyl ester 

Downstream Products

• 330944-31-5 (4-methyl)-3-pentenyl (S)-2-[(1,1-dimethylethyl)diphenylsilyl]oxypropanoate 
• 330944-29-1 (1S)-1-[(4-methyl)pent-3-enyloxycarbonyl]ethyl 3-oxocyclohex-1-enecarboxylate 

Relevant academic research and scientific papers

Copper-Catalyzed Reductive Ireland-Claisen Rearrangements of Propargylic Acrylates and Allylic Allenoates

The copper-catalyzed reductive Ireland-Claisen rearrangement of propargylic acrylates led to 3,4-allenoic acids. The use of silanes or pinacolborane as stoichiometric reducing agents and triethylphosphite as a ligand facilitated the divergent and complementary selectivity for the synthesis of diastereomeric anti- and syn-rearranged products, respectively. Copper-catalyzed reductive Ireland-Claisen rearrangement of allylic 2,3-allenoates proceeded effectively only when pinacolborane was used as a reductant to generate various 1,5-dienes in excellent yields and with good diastereoselectivities in some cases. Mechanistic studies showed that the silyl and boron enolates, rather than the copper enolate, underwent a stereospecific rearrangement via a chairlike transition state to afford the corresponding Claisen rearrangement products.

Novel ruthenium-catalyst for hydroesterification of olefins with formates

An alternative ruthenium-based catalyst for the hydroesterification of olefins with formates is reported. The good activity of our system is ensured by the use of a bidentate P,N-ligand and ruthenium dodecacarbonyl. A range of formates can be used for selective alkoxycarbonylation of aromatic olefins. In addition, the synthesis of selected aliphatic esters is realized. The proposed active ruthenium complex has been isolated and characterized. This journal is the Partner Organisations 2014.

Palladium-catalyzed alkoxycarbonylation of conjugated dienes under acid-free conditions: Atom-economic synthesis of β,γ-unsaturated esters

Carbonylation reactions constitute important methodologies for the synthesis of all kinds of carboxylic acid derivatives. The development of novel and better catalysts for these transformations is of interest for both academic and industrial research. Here, a benign palladium-based catalyst system for the alkoxycarbonylation of conjugated dienes under acid-free conditions has been developed. This atom-efficient transformation provides straightforward access to a variety of β,γ-unsaturated esters in good to excellent yields and often with high selectivities. As an industrially relevant example the (formal) synthesis of dimethyl adipate and ε-caprolactam from 1,3-butadiene is demonstrated.

Radical allylation, vinylation, alkynylation, and phenylation reactions of α-halo carbonyl compounds with organoboron, organogallium, and organoindium reagents

Allylic gallium and indium reagents are found to mediate radical allylation reactions of α-iodo or α-bromo carbonyl compounds. Treatment of benzyl bromoacetate with allylgallium, prepared from allylmagnesium chloride and gallium trichloride, in the presence of triethylborane provided benzyl 4-pentenoate in excellent yield. Addition of water as a co-solvent improved the yields of allylated products. Allylic indium reagents are also useful and can replace the gallium reagents. A diallylborane reagent can allylate an α-iodo ester in good yield. Alkenylation reactions of α-halo carbonyl compounds with alkenylindium proceeded via a radical process in the presence of triethylborane. Unactivated alkene moieties and styryl groups were introduced by this method. The carbon-carbon double bond geometry of the alkenylindiums was retained during the alkenylation. Preparation of an alkenylindium via a hydroindation of 1-alkyne and subsequent radical alkenylation established an efficient one-pot strategy. Radical alkynylations and phenylations with organoindium reagents are disclosed herein.

Radical alkenylation of α-halo carbonyl compounds with alkenylindiums

(Chemical equation presented) Alkenylation reaction of α-halo carbonyl compounds with alkenylindiums proceeded via a radical process in the presence of triethylborane. Unactivated alkene moieties as well as a styryl group could be introduced by this metho

Application of chiral tethers to intramolecular [2 + 2] photocycloadditions: Synthetic approach to (-)-italicene and (+)-isoitalicene

A synthetic approach to (-)-italicene and (+)-isoitalicene, sesquiterpenes which possess the rare tricyclo[5.4.0.01,5] undecane skeleton has been developed using a key step a highly regio- and diastereoselective [2 + 2] photocycloaddition. (S)-