83173-76-6

Upstream product

• 4784-77-4 (E)-1-Bromo-2-butene 
• 104-87-0 4-methyl-benzaldehyde 
• 35998-93-7 tri-n-butylcrotyltin 
• 21969-32-4 crotylmagnesium chloride 
• 4894-61-5 trans-but-2-enyl chloride 
• 1122-91-4 4-bromo-benzaldehyde 
• 4784-77-4 (E/Z)-crotyl bromide 
• 504-61-0 (E)-but-2-enol 
• 31197-41-8 crotyltributylstannane 
• 106-99-0 buta-1,3-diene 
• 1458-98-6 2-methyl-3-bromo-1-propene 
• 107-01-7 butene-2 
• 1357478-15-9 (±)-2-(but-3-en-2-yl)-5,5-dimethyl-1,3,2-dioxaborinane 
• 35998-94-8 (Z)-crotyltri-n-butylstannane 

Relevant academic research and scientific papers

Allylation and propargylation of aldehydes mediated byin situgenerated zinc from the redox couple of Al and ZnCl2in 2N HCl

A simple one pot allylation and propargylation of aldehydes mediated by zinc(0), which isin situgenerated from the redox couple of Al and ZnCl2in 2N HCl, is demonstrated to afford the corresponding homoallyl and homopropargyl alcohols with exce

Catalytic Allylation of Aldehydes Using Unactivated Alkenes

Simple feedstock organic molecules, especially alkenes, are attractive starting materials in organic synthesis because of their wide availability. Direct utilization of such bulk, inert organic molecules for practical and selective chemical reactions, however, remains limited. Herein, we developed a ternary hybrid catalyst system comprising a photoredox catalyst, a hydrogen-atom-transfer catalyst, and a chromium complex catalyst, enabling catalytic allylation of aldehydes with simple alkenes, including feedstock lower alkenes. The reaction proceeded under visible-light irradiation at room temperature and with high functional group tolerance. The reaction was extended to an asymmetric variant by employing a chiral chromium complex catalyst.

Photoredox Ni-Catalyzed Branch-Selective Reductive Coupling of Aldehydes with 1,3-Dienes

We report here a Ni-catalyzed reductive coupling of aldehydes with widely available 1,3-dienes under visible-light photoredox dual catalysis. The homoallyic alcohols are obtained in broad scope with complete branched regioselectivity. Hantzsch ester is used as the hydrogen radical source to oxidize low-valent nickel salt affording Ni-H species. Preliminary mechanistic studies indicate a successive single-electron transfer (SET) pathway and the generation of a key π-allylnickel intermediate via Ni-H insertion of 1,3-diene in this synergistic catalytic process.

Active bismuth mediated allylation of carbonyls/N-tosyl aldimines and propargylation of aldehydes in water

Abstract: Active bismuth is synthesized by the chemical reduction of bismuth trichloride using freshly prepared sodium stannite solution as the reducing agent at room temperature. The as-synthesized active bismuth is applied as a reagent for the synthesis of homoallyl alcohol/homopropargyl alcohol from allyl bromide/propargyl bromide and carbonyl compounds in water at 50°C. The homoallyl amines are also synthesized from N-tosyl aldimines and allyl bromide using active bismuth reagent in good yields. No assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere is required for this reaction. The waste bismuth material obtained after the completion of the organic reaction can be reduced to active bismuth by sodium stannite solution and successfully reused for mediating the allylation of aldehydes. Graphical Abstract:: Synopsis Active bismuth mediated allylation/crotylation of aldehydes is developed in water to get homoallyl alcohols. The method is also applied for the allylation of N-tosyl aldimines and propargylation of aldehydes in water to achieve the homoallyl amines and homopropargyl alcohols, respectively. The reactions do not require the assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere.[Figure not available: see fulltext.].

Catalytic organic reactions on the surface of silver(I) oxide in water

We have developed Ag2O-catalyzed allylation reactions of aldehydes with allylsilanes in water, providing homoallylic alcohols in high yields with high anti-selectivities. It was found that the reactions proceeded not in the water solution but o

Allylation reactions of aldehydes with allylboronates in aqueous media: Unique reactivity and selectivity that are only observed in the presence of water

Zn(OH)2-catalyzed allylation reactions of aldehydes with allylboronates in aqueous media have been developed. In contrast to conventional allylboration reactions of aldehydes in organic solvents, the α-addition products were obtained exclusively. A catalytic cycle in which the allylzinc species was generated through a B-to-Zn exchange process is proposed and kinetic studies were performed. The key intermediate, an allylzinc species, was detected by HRMS (ESI) analysis and by online continuous MS (ESI) analysis. This analysis revealed that, in aqueous media, the allylzinc species competitively reacted with the aldehydes and water. An investigation of the reactivity and selectivity of the allylzinc species by using several typical allylboronates (6a, 6b, 6c, 6d) clarified several important roles of water in this allylation reaction. The allylation reactions of aldehydes with allylboronic acid 2,2-dimethyl-1,3-propanediol esters proceeded smoothly in the presence of catalytic amounts of Zn(OH)2 and achiral ligand 4d in aqueous media to afford the corresponding syn-adducts in high yields with high diastereoselectivities. In all cases, the α-addition products were obtained and a wide substrate scope was tolerated. Furthermore, this reaction was applied to asymmetric catalysis by using chiral ligand 9. Based on the X-ray structure of the Zn-9 complex, several nonsymmetrical chiral ligands were also found to be effective. This reaction was further applied to catalytic asymmetric alkylallylation, chloroallylation, and alkoxyallylation processes and the synthetic utility of these reactions has been demonstrated. Still waters run deep: The Zn(OH)2-catalyzed allylation of aldehydes with allylboronates in aqueous media exclusively afford the α-addition products. This reaction was also applied to alkylallylation, chloroallylation, and alkoxyallylation reactions. The role of water is discussed. Copyright

Gallium-mediated allyl transfer from bulky homoallyl alcohol to aldehydes or alkynes: Control of dynamic σ-allylgalliums based on retro-allylation reaction

A new method for the preparation and control of dynamic σ-allylgalliums is disclosed. Upon treatment with a Grignard reagent and gallium trichloride, bulky homoallyl alcohols undergo gallium-mediated retro-allylation reaction to provide σ-allylgallium reagents. The σ-allylgallium reagents generated were applied to carbonyl allylation. The retro-allylation reaction generates (Z)- and (E)-σ-crotylgalliums stereospecifically, starting from erythro- and threo-homoallyl alcohols, respectively. The stereochemically defined crotylgallium reagents effected stereoselective allylation of aldehydes. Allylgallation reaction of alkynes with the allylgallium reagents prepared by retro-allylation is also described.

The employment of indium nanoparticles in Barbier-type reaction of allylic chloride in water

Indium nanoparticles have been employed in the reactions of various carbonyl compounds with allyl (crotyl) chloride in water, affording the corresponding alcohols with high yields. The crotylation gave exclusive γ-adducts with a dominant syn-isomer. Copyr

Allylation of aldehydes promoted by the cerium(III) chloride heptahydrate/sodium iodide system: The dependence of regio- and stereocontrol on the reaction conditions

The cerium(III) chloride heptahydrate/sodium iodide complex (CeCl 3·7 H2O/NaI) acts as a useful promoter in the carbon-carbon bond forming reaction by addition of allyltributylstannanes to aldehydes. The reaction of 2-butenyltributyl

Gallium-mediated allyl transfer from bulky homoallylic alcohol to aldehydes via retro-allylation: Stereoselective synthesis of both erythro- and threo-homoallylic alcohols

(Chemical Equation Presented) Retro-allylation of bulky gallium homoallylic alkoxides occurs to generate (Z)- and (E)-crotylgallium reagents stereospecifically, starting from erythro- and threo-homoallylic alcohols, respectively. The (Z)- and (E)-crotylgallium reagents immediately reacted with aromatic aldehydes to afford the corresponding erythro and threo-homoallylic alcohols, respectively.