86361-20-8

Upstream product

• 128291-28-1 2'-isopropenylpotassium 
• 100-52-7 benzaldehyde 
• 1335316-66-9 4,4,5,5-tetramethyl-2-(2-methylenebut-3-enyl)-1,3,2-dioxaborolane 
• 13429-21-5 2-methylene-3-buten-1-ol 
• 70901-64-3 trimethyl(2-methylenebut-3-enyl)silane 
• 100363-61-9 2-Dipropylborylmethyl-1,3-butadiene 
• 130540-33-9 B-isoprenyl-9-borabicyclo<3.3.1>nonane 
• 78-79-5 isoprene 
• 1826-67-1 vinyl magnesium bromide 
• 87763-90-4 3-bromo-1-phenyl-but-3-en-1-ol 
• 16526-19-5 (E)-1,4-dibromo-2-methylbut-2-ene 
• 83889-55-8 1,4-dibromo-2-(bromomethyl)but-2-ene 
• 111558-76-0 Trimethyl-(3-methylene-1-phenyl-pent-4-enyloxy)-silane 

Relevant academic research and scientific papers

Enantioselective Isoprenylboration Reaction of Aldehydes Catalyzed by a Chiral Phosphoric Acid

The BINOL-derived chiral phosphoric acid (R)-TRIP is utilized as an organocatalyst in the asymmetric isoprenylboration reaction of aldehydes, wherein hydrogen-bond interactions play a key role in the control of enantioselectivity. A wide arrays of enantioenriched dienyl homoallyl alcohols, including two natural products (?)-Ipsdienol and (?)-Ipsenol, have been successfully constituted. The synthetic application to chiral isoprenylated isobenzofuranone, vinyloxirane and cyclohexene derivatives has also been disclosed. (Figure presented.).

1,4-hydroiodination of dienyl alcohols with tmsi to form homoallylic alcohols containing a multisubstituted Z -alkene and application to prins cyclization

A regioselective 1,4-hydroiodination of dienyl alcohols has been developed using trimethylsilyl iodide as Lewis acid and iodide source. A range of homoallylic alcohols containing a multisubstituted Z-alkene was synthesized with good to excellent configurational control. The approach was applied in sequential hydroiodination/Prins cyclization to afford multisubstituted tetrahydropyrans diastereoselectively.

TMSBr/InBr3-promoted Prins cyclization/homobromination of dienyl alcohol with aldehyde to construct cis-THP containing an exocyclic E-alkene

A TMSBr/InBr3-promoted Prins cyclization/homobromination reaction of dienyl alcohol with aldehyde has been developed to construct a unique cis-E THP shown as the A ring in (-)-exiguolide and the B ring in bryostatins.

Dienyl homoallyl alcohols via palladium catalyzed ene-type reaction of aldehydes with 1,3-dienes

The combination of Pd catalyst and Xantphos ligand in the presence of Et3B nicely promotes the allylation of aldehydes with conjugated dienes to provide dienyl homoallyl alcohols in excellent yields. The reaction occurs selectively at the C-C double bond bearing higher electron density.

Catalytic asymmetric allylic transfer reactions for the Enantioselective synthesis of dienyl and enynyl alcohols

Efficient catalytic asymmetric allylic transfer reactions of achiral aldehydes with 2-ethynyl- and 2-ethenyl-2-propenyl-stannane promoted by BINOL-TiIV complex with synergetic reagent are achieved for the synthesis of homoenynyl- and dienyl alcohols with high levels of enantioselectivity. The range of enantioselectivity is 84-99% ee with good chemical yields. The application of catalytic asymmetric dienylation in a single operation was exemplified by the enantioselective synthesis of naturally occurring (-)-Ipsdienol and (-)-Ipsenol.

New preparation of reactive zinc metal by electrolysis and its use for a facile isoprenylation of aldehydes and ketones

Reactive zinc metal can be prepared by the electrolysis of a DMF solution containing Et4NClO4 with a platinum cathode and a zinc anode. The reaction of 2-bromomethyl-1, 4-dibromo-2-butene (1) with aldehydes or ketones in the presence of the electrogenarated reactive zinc (EGZn) in DMF at 0 °C gave the corresponding isoprenylated alcohols (3a-3n) in good yields.

Convenient isoprenylation of aldehydes and ketones: Synthesis of (±)-ipsdienol and (±)-ipsenol

The reaction of 2-bromomethyl-1,4-dibromo-2-butene (1) with various aldehydes and ketones in tetrahydrofuran containing zinc powder under reflux gave the corresponding isoprenylated alcohols 3a-o in one step in good yields. The synthesis of ipsdienol (3e) and ipsenol (3c) was achieved by the present method starting from 3-methyl-2-butenal (2e) and isovaleraldehyde (2c).

In Turn or in Reverse Palladium-Catalyzed Carbonyl Allylation and Diels-Alder Reaction by 2-Methylene-3-buten-1-ol

Using PdCl2(PhCN)2-SnCl2, 2-methylene-3-buten-1-ol causes carbonyl allylation of various aldehydes to afford 1-substituted-3-methylene-4-penten-1-ols, the Diels-Alder reaction of those with dienophiles produces 1-(2-hydroxyethyl)cyclohexenes.Diels-Alder reaction of 2-methylene-3-buten-1-ol with dienophiles followed by carbonyl allylation produces isomeric 1-methylene-2-(hydroxymethyl)cyclohexanes.

Intermediates useful for the chiral isoprenylation of aldehydes

An improved process for preparing either optically pure enantiomer of the bark beetle pheromones ipsenol and ipsdienol is provided. The process is also applicable to the condensation of aldehydes of widely varying properties to the corresponding chiral alcohol. This invention also concerns novel intermediates R'2 B(2'-isoprenyl) wherein R' is isopinocampheyl, 2-isocaranyl and 4-isocaranyl.

Chiral synthesis VIA organoboranes. 26. An efficient synthesis of isoprenyl derivatives of borane - Valuable reagents for the isoprenylboration of aldehydes. A convenient route to both enantiomers of ipsenol and ipsdienol in high optical purity

Preparation of B-isoprenyldialkylboranes is achieved by adopting the Brandsma modification of the Schlosser procedure, namely metallation of isoprene with potassium 2,2,5,5-tetramethylpiperidide followed by sequential treatment with 5-methoxydialkylborane and boron trifluoride-etherate. These reagents are used for the convenient isoprenylation of aldehydes. Reaction of isovaleraldehyde and β, β-dimethylacrolein with B2′isoprenyldiisopinocampheylborane provides both ipsenol and ipsdienol, respectively in 65% yields and 96% ee.