87938-63-4

Upstream product

• 19319-26-7 (Z)-2-methyl-2-buten-1-ol 
• 100-52-7 benzaldehyde 
• 497-02-9 (E)-2-methyl-2-buten-1-ol 
• 78-79-5 isoprene 
• 91495-68-0 3-benzyloxy-2-methyl-1-butene 
• 94235-21-9 Benzoic acid (Z)-2-methyl-but-2-enyl ester 
• 94235-22-0 (E)-2-methylbut-2-en-1-yl benzoate 
• 87938-71-4 C₁₁H₂₁BO₂ 
• 33425-30-8 Essigsaeure-<(E)-2-methyl-2-butenyl>ester 

Relevant academic research and scientific papers

Reversal of Anti to Syn Diastereoselectivity in Crotyltitanation Reaction

η3-2-Methylcrotyl(tiglyl)titanocene reacts with aldehydes to afford anti homoallylic alcohols when the reaction is carried out in THF, and preferentially syn products when the solvent is HMPA/THF=3:1. This simple control of anti versus syn dias

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.

Ni- and pd-catalyzed synthesis of substituted and functionalized allylic boronates

Two highly efficient and convenient methods for the synthesis of functionalized and substituted allylic boronates are described. In one procedure, readily available allylic acetates are converted to allylic boronates catalyzed by Ni/PCy3 or Ni/PPh3 complexes with high levels of stereoselectivity and in good yields. Alternatively, the borylation can be accomplished with commercially available Pd catalysts [e.g., Pd 2(dba)3, PdCl2, Pd/C], starting with easily accessed allylic halides.

Rh-catalyzed reductive coupling reaction of aldehydes with conjugated dienes promoted by triethylborane

Rh(I) catalyzes the reductive coupling reaction of a wide variety of aldehydes with conjugated dienes in the presence of a stoichiometric amount of triethylborane to provide homoallyl alcohols in a single operation.

Unique regio- and stereoselectivity in the allylation of benzaldehyde with 2-substituted allylzincs generated by umpolung of π-allylpalladium

α,β-Disubstituted allylzincs with alkoxycarbonyl as the β-substituent, generated via an umpolung of in situ generated π-allylpalladium by transmetallation with diethylzinc, react with benzaldehyde at the most substituted allylic terminus to provide syn-γ-

One-pot synthesis of homoallylic alcohols from 1,3-dienes: Tandom vicinal difunctionalization of 1,3-dienes by hydride addition-aldehyde coupling sequence via organosilicon intermediates

Homoallylic alcohols were directly prepared from 1,3-dienes in high yields with high regio- and stereoselectivity. The process consists of a hydride addition-aldehyde coupling sequence via organosilicon intermediates (an example of tandem vicinal difuncti

First Practical Hydrozincation of Dienes Catalyzed by Cp2TiCl2. Generation of Allylzinc Reagent and Its Reaction with Carbonyl Compounds

The first practical hydrozincation of butadiene and 2-alkylbutadienes has been achieved by a combination reagent including ZnI2, LiH, and Cp2TiCl2 in a ratio of 1:2.2:0.1 to yield the corresponding allylzinc reagents in THF, which, in turn, react with a variety of carbonyl compounds.

Palladium-catalyzed carbonyl allylation by allylic alcohols with SnCl2

Allylic alcohols can be applied to carbonyl allylation via the formation of π-allylpalladium complexes, using palladium as catalyst and SnCl2 as a reducing agent. This reaction has chemoselectivity: The reactivity order of allylating agents is allylic carbonate > allylic alcohol > allylic acetate, and that of carbonyl compounds is aldehyde > ketone. High regioselcction was observed in polar solvents such as DMF, DMI, and DMSO; carbonyl compounds apparently attacked the more substituted allylic position of π-allylpalladium complexes to afford only one regioisomer. Diastereocontrol in the carbonyl allylation of aromatic aldehydes by (E)-2-butenol was achieved by the choice of polar solvents; use of DMSO at 25 °C led to syn selection, while anti selection was found at -10 °C in THF. The addition of H2O in any solvent accelerated the carbonyl allylation and enhanced both regioselectivity and the diastereoselectivity. Anti selection in DMF, DMI, and THF-H2O can be explained by the chair form of the six-membered cyclic transition state, while syn selection in DMSO allows us to propose an acyclic antiperiplanar transition state. An NMR spectroscope investigation demonstrated that the actual allylating agent in dry medium was allyltrichlorotin: 1H, 13C, and 119Sn NMR spectra of the reaction of allyl alcohol with PdCl2(PhCN)2-SnCl2 in DMF-d7. corresponded to those of the reaction of allyl chloride with PdCl2(PhCN)2-SnCl2 in DMF-d7.

NEW CONVENIENT APPROACH TO THE PREPARATION OF (Z)-ALLYLIC BORONATES VIA CATALYTIC 1,4-HYDROBORATION OF 1,3-DIENES WITH CATECHOLBORANE

Hydroboration of 1,3-butadiene, isoprene, myrcene, 2,3-dimethyl-1,3-butadiene, and 1,3-cyclohexadiene with catecholborane(1,3,2-benzodioxaborole) in the presence of Pd(PPh3)4 or Rh4(CO)12 catalysts proceeds smoothly to provide 2--1,3,2-benzodioxaboroles in very high regio- and stereoselectivity.

PALLADIUM-CATALYZED CARBONYL ALLYLATION BY ALLYLIC ALCOHOLS WITH SnCl2. A SOLVATION-CONTROLLED DIASTEREOSELECTION

Diastereocontrol in the allylation of benzaldehyde by (E)-but-2-en-1-ol using catalyst PdCl2(PhCN)2 and SnCl2 was achieved by the choice of polar solvents; use of DMSO at 25 deg C led to syn selection, while anti selection was found at -10 deg C in THF.Th