83173-74-4

Upstream product

• 104-53-0 3-phenyl-propionaldehyde 
• 4784-77-4 (E)-1-Bromo-2-butene 
• 99687-40-8 (R,R)-[(E)-2-butenyl]diisopropyl tartrate boronate 
• 18147-55-2 (E)-crotyltrichlorosilane 
• 804559-38-4 (R,R)-crotylsilane 
• 804559-39-5 (R,R)-trans EZ-CrotylMix 
• 69611-01-4 (Z)-2-(but-2-enyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 69611-02-5 (E)-2-(but-2-enyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 6737-11-7 2-acetoxy-3-butene 
• 122-97-4 3-Phenyl-1-propanol 
• 1280227-81-7 (3R,4S,E)-4-methyl-1-phenyl-6-(tributylstannyl)hex-5-en-3-ol 
• 4784-77-4 (E/Z)-crotyl bromide 
• 1004996-53-5 C₁₄H₂₃BO₆ 
• 4894-61-5 trans-but-2-enyl chloride 

Downstream Products

• 518308-57-1 (2S,3R)-2-methyl-5-phenylpentane-1,3-diol 
• 261919-07-7 (3S,5E)-1-phenyl-5-heptene-3-ol 
• 1615707-74-8 C₁₅H₂₂O₄ 
• 1615707-75-9 C₃₁H₄₀O₄Si 
• 1615707-76-0 tert-butyldiphenyl(((4R,5R,6R)-2,2,5-trimethyl-6-phenethyl-1,3-dioxan-4-yl)methoxy)silane 
• 1615707-40-8 C₂₅H₄₂B₂O₅ 
• 1615707-42-0 (3R,4S,5S)-4-methyl-1-phenyl-5,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexan-3-yl acetate 
• 1615707-73-7 (3R,4S)-4-methyl-1-phenylhex-5-en-3-yl acetate 

Relevant academic research and scientific papers

Cp2TiCl2-Catalyzed Photoredox Allylation of Aldehydes with Visible Light

A Barbier-type Cp2TiCl2-mediated (10 mol %) photoredox allylation of aldehydes under irradiation with visible light (blue light-emitting diodes (LEDs), 450 nm) and in the presence of an organic dye (3DPAFIPN, 5 mol %) with allylbromides is described.

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.

Direct, Mild, and General n-Bu4NBr-Catalyzed Aldehyde Allylsilylation with Allyl Chlorides

A direct, mild, and general method for the enantioselective allylsilylation of aldehydes with allyl chlorides is reported. The reactions are effectively catalyzed by 5 mol % of n-Bu4NBr, and this rate acceleration allows the use of complex allyl donors in fragment-coupling reactions and of electron-deficient allyl donors. The results are (1) significant progress toward a "universal" asymmetric aldehyde allylation reaction that can reliably and highly stereoselectively couple any allyl chloride-aldehyde combination and (2) the discovery of a novel mode of nucleophilic catalysis for aldehyde allylsilylation reactions.

Transition-metal-free reductive coupling of 1, 3-butadienes with aldehydes catalyzed by dibutyliodotin hydride

In this study, the Bu2SnIH-catalyzed direct coupling of 1, 3- dienes with aldehydes was developed. This reaction could be suitable for coupling without the use of transition-metal catalysts. Many types of aldehydes were applied to this reaction. The addition of MeOH promoted the catalytic cycle.

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.

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

Ping-pong polymerization by allylation and hydroformylation for alternating vinyl alcohol-vinyl monomer copolymers

Inspired by the enzymatic ping-pong mechanism, we designed a novel ping-pong polymerization , which employs allylation and hydroformylation in an iterative and alternating manner. Thus, alternating and regioregular vinyl alcohol-vinyl monomer copolymers possessing multiple hydroxy groups in a periodical manner were successfully synthesized.

Highly stereoselective synthesis of anti, anti -dipropionate stereotriads: A solution to the long-standing problem of challenging mismatched double asymmetric crotylboration reactions

The stereocontrolled synthesis of the β-branched anti,anti- dipropionate stereotriad 4 via aldol or crotylmetal chemistry represents a historical challenge to the organic synthesis community. Here we describe a general solution to the long-standing problem associated with the synthesis of 4 by utilizing mismatched double asymmetric crotylboration reactions of enantioenriched α-methyl substituted aldehydes with the chiral, nonracemic crotylborane reagent (S)-(E)-22 (or its enantiomer). This method not only provides direct access to anti,anti-dipropionate stereotriads 24 [a synthetic equivalent of 4] with very good (5-8:1) if not excellent (≥15:1) diastereoselectivity from β-branched chiral aldehydes with ≥50:1 intrinsic diastereofacial selectivity preferences but also provides a vinylstannane unit in the products that is properly functionalized for use in subsequent C-C bond-forming events. We anticipate that this method will be widely applicable and will lead to substantial simplification of strategies for synthesis of polyketide natural products.

COMPOSITIONS AND METHODS FOR STEREOSELECTIVE ALDEHYDE ALLYLATION AND CROTYLATION

Compositions and methods for practical, stereoselective allylation and crotylation for aldehyde substrates are described. The compositions and methods comprise reagents for allylation and/or crotylation and acids. In some embodiments, the reagents and acids are pre-mixed.