136033-30-2

Upstream product

• 504-61-0 (E)-but-2-enol 
• 123-11-5 4-methoxy-benzaldehyde 
• 35998-93-7 tri-n-butylcrotyltin 
• 35998-94-8 (Z)-crotyltri-n-butylstannane 
• 6737-11-7 2-acetoxy-3-butene 
• 105-13-5 4-Methoxybenzyl alcohol 
• 76505-19-6 tributyl(1-methyl-2-propenyl)stannane 
• 106-99-0 buta-1,3-diene 
• 1357478-15-9 (±)-2-(but-3-en-2-yl)-5,5-dimethyl-1,3,2-dioxaborinane 
• 31197-41-8 crotyltributylstannane 
• 4894-61-5 trans-but-2-enyl chloride 
• 4784-77-4 (E/Z)-crotyl bromide 
• 18147-55-2 (Z)-crotyltrichlorosilane 
• 21969-32-4 crotylmagnesium chloride 

Relevant academic research and scientific papers

A Mild Protocol for Allylation and Highly Diastereoselective Syn or Anti Crotylation of Aldehydes in Biphasic and Aqueous Media Utilizing Potassium Allyl- and Crotyltrifluoroborates

(Equation Presented) Potassium allyl- and crotyltrifluoroborates undergo addition to aldehydes in biphasic media as well as water to provide the corresponding homoallylic alcohols in high yields (≥94%), excellent diastereoselectivity (dr ≥ 98:2), and with

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.

Syn -Selective crotylation of aldehydes using bismuth-crotyl bromide-(1-butyl-3-methylimidazolium bromide) combination: Some synthetic applications

The Bi-[bmim][Br] combination has been found to offer high syn-selectivity in the crotylation of aldehydes with crotyl bromide using practically stoichiometric amounts of the reagents. The room temperature ionic liquid (RTIL), [bmim][Br], activated Bi metal in the presence of oxygen to produce crotylbismuthdibromide, which reacted with the aldehydes at room temperature. The major anti-syn diastereomeric product obtained from the crotylation of (R)-cyclohexylideneglyceraldehyde was utilized for the synthesis of dictyostatin and cryptophycin segments, and (+)-cis-aerangis lactone, using standard synthetic protocols.

Nickel-catalyzed double bond transposition of alkenyl boronates for in situ syn-selective allylboration reactions

The transposition of a homoallyl pinacol boronic ester was realized by a highly reactive nickel-catalyst system comprising NiCl2(dppp), zinc powder, ZnI2, and Ph2PH. The in situ generated Z-crotyl pinacol boronic esters were reacted with various aldehydes to form syn-homoallylic alcohols in high diastereoselectivities. The present nickel-catalyzed reaction is complementary to the iridium-catalyzed transposition reported by Murakami leading to the corresponding anti-homoallylic alcohols. Also, the multiple transposition of pentenyl pinacol boronic ester was realized.

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

Silver oxide as a novel catalyst for carbon-carbon bond-forming reactions in aqueous media

Silver oxide was found to be an excellent catalyst for allylation reactions of allyltributyltins with aldehydes in aqueous media. Despite the very low solubility of silver oxide in the media, the reactions proceeded smoothly, and the catalyst was recovere

Allylation and crotylation of ketones and aldehydes using potassium organotrifluoroborate salts under lewis acid and montmorillonite k10 catalyzed conditions

Two convenient highly diastereoselective protocols for the allylation and crotylation of ketones using practical, air- and water-stable potassium allyl and crotyltrifluoroborate salts have been developed. BF3-OEt 2 and montmorillonit

Enantioselective iridium-catalyzed carbonyl allylation from the alcohol or aldehyde oxidation level using allyl acetate as an allyl metal surrogate

Protocols for highly enantioselective carbonyl allylation from the alcohol or aldehyde oxidation level are described based upon transfer hydrogenative C-C coupling. Exposure of allyl acetate to benzylic alcohols 1a-i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (R)-BINAP delivers products of C-allylation 2a-i. Employing isopropanol as terminal reductant, exposure of allyl acetate to aryl aldehydes 3a-i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (-)-TMBTP delivers identical products of C-allylation 2a-i. In all cases examined, exception levels of enantioselectivity are observed. Thus, enantioselective carbonyl allylation is achieved from the alcohol or aldehyde oxidation level in the absence of any preformed allylmetal reagents. These studies define a departure from preformed organometallic reagents in carbonyl additions that transcend the boundaries of oxidation level. Copyright

On the mechanism of asymmetric allylation of aldehydes with allyltrichlorosilanes catalyzed by QUINOX, a chiral isoquinoline N-oxide

Allylation of aromatic aldehydes 1a-m with allyl- and crotyl- trichlorosilanes 2-4, catalyzed by the chiral N-oxide QUINOX (9), has been found to exhibit a significant dependence on the electronics of the aldehyde, with p-(trifluoromethyl)benzaldehyde 1g