77383-08-5

Upstream product

• 556-56-9 allyl iodid 
• 2550-26-7 4-Phenyl-2-butanone 
• 591-87-7 Allyl acetate 
• 106-95-6 allyl bromide 
• 104-53-0 3-phenyl-propionaldehyde 
• 7393-43-3 tetraallyl tin 
• 35466-83-2 allyl methyl carbonate 
• 18854-66-5 tris(allyl)aluminum 
• 72824-04-5 2-Allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 2653-46-5 allyl 4-methylbenzoate 
• 329-81-7 allyl 4-(trifluoromethyl)benzoate 
• 107-05-1 3-chloroprop-1-ene 
• 165904-22-3 4,4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane 
• 911482-75-2 allylboronic acid 2,2-dimethyl-1,3-propanediol ester 

Downstream Products

• 92101-05-8 (±)-3-methyl-1-phenylhexan-3-ol 

Relevant academic research and scientific papers

CpTiCl2, an Improved Titanocene(III) Catalyst in Organic Synthesis

Preparation, EPR analysis, and advantages in green organic chemistry of CpTiCl2, an improved single-electron transfer catalyst, are reported. Under mild conditions, this organometallic complex provides excellent yields of homoallylic and homopropargylic alcohols in Barbier-type allylation and propargylation reactions. Moreover, in the presence of a bidentate BOX ligand, Barbier-type cyclization reactions catalyzed by CpTiCl2 can be carried out in an enantioselective manner.

α-Sulfinyl Benzoates as Precursors to Li and Mg Carbenoids for the Stereoselective Iterative Homologation of Boronic Esters

The stereoselective reagent-controlled homologation of boronic esters is one of a small number of iteratable synthetic transformations that if automated could form the basis of a veritable molecule-making machine. Recently, α-stannyl triisopropylbenzoates and α-sulfinyl chlorides have emerged as useful building blocks for the iterative homologation of boronic esters. However, α-stannyl benzoates need to be prepared using stoichiometric amounts of the (+)- or (-)-enantiomer of the scarcely available and expensive diamine sparteine; also, these building blocks, together with the byproducts that are generated during homologation, are perceived as being toxic. On the other hand, α-sulfinyl chlorides are difficult to prepare with high levels of enantiopurity and are prone to undergo deleterious acid-base side-reactions under the reaction conditions for homologation, leading to low stereospecificity. Here, we show that the use of a hybrid of these two building blocks, namely, α-sulfinyl triisopropylbenzoates, largely overcomes the above drawbacks. Through either the sulfinylation of α-magnesiated benzoates with either enantiomer of Andersen's readily available menthol-derived sulfinate or the α-alkylation of enantiopure S-chiral α-sulfinyl benzoates, we have prepared a range of highly enantiopure mono- and disubstituted α-sulfinyl benzoates, some bearing sensitive functional groups. Barbier-type reaction conditions have been developed that allow these building blocks to be converted into lithium (t-BuLi) and magnesium (i-PrMgCl·LiCl) carbenoids in the presence of boronic esters, thus allowing efficient and highly stereospecific homologation. The use of magnesium carbenoids allows carbon chains to be grown with the incorporation of sensitive functional groups, such as alkyl/aryl halides, azides, and esters. The use of lithium carbenoids, which are less sensitive to steric hindrance, allows sterically encumbered carbon-carbon bonds to be forged. We have also shown that these building blocks can be used consecutively in three- and four-step iterative homologation processes, without intervening column chromatography, to give contiguously substituted carbon chains with very high levels of enantio- and diastereoselectivity.

Nickel-catalyzed reductive allylation of ketones with allylic carbonates

Nickel-catalyzed efficient umpolung allylation of ketones with allylic carbonates in the presence of zinc powder is developed, which accommodates a variety of allylic and ketone substrates. Although chiral ligand is necessary for the transformation, no enantioselectivity was observed. Georg Thieme Verlag Stuttgart New York.

Asymmetric allylation of ketones and subsequent tandem reactions catalyzed by a novel polymer-supported titanium-binolate complex

By using a novel, simple, and convenient synthetic route, enantiopure 6-ethynyl-BINOL (BINOL=1,1-binaphthol) was synthesized and anchored to an azidomethylpolystyrene resin through a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction. The polyst

Cooperative titanocene and phosphine catalysis: Accelerated C-X activation for the generation of reactive organometallics

The study presented herein describes a reductive transmetalation approach toward the generation of Grignard and organozinc reagents mediated by a titanocene catalyst. This method enables the metalation of functionalized substrates without loss of functional group compatibility. Allyl zinc reagents and allyl, vinyl, and alkyl Grignard reagents were generated in situ and used in the addition to carbonyl substrates to provide the corresponding carbinols in yields up to 99%. It was discovered that phosphine ligands effectively accelerate the reductive transmetalation event to enable the metalation of C-X bonds at temperatures as low as -40 °C. Performing the reactions in the presence of chiral diamines and amino alcohols led to the enantioselective allylation of aldehydes.

Porous and robust lanthanide metal-organoboron frameworks as water tolerant Lewis acid catalysts

Porous and robust 12-connected metal-organic frameworks (MOFs) were constructed by linking tetranuclear lanthanide (Ln) carbonate clusters with organoboron-derived tricarboxylate bridging ligands. The high-connectivity Ln-MOFs feature remarkable thermal a

Use of electrochemistry to provide efficient SmI2 catalytic system for coupling reactions.

Samarium metal has been used for the first time as electrode material to perform as an efficient and versatile SmI2 catalytic system assisted by electrochemistry. The established electrocatalytic procedure that excludes any metal additives was successfully applied in various transformations mediated by this useful reagent.

Catalytic use of zinc amide for transmetalation with allylboronates: General and efficient catalytic allylation of carbonyl compounds, imines, and hydrazones

The efficient catalytic allylation of ketones, imines, and hydrazones with allylboronates using a catalytic amount of zinc amide is reported. In this reaction, the boron-to-zinc exchange process occurred smoothly to afford the corresponding allylzinc amides, and the desired allylation reactions proceeded in high efficiency (～0.1mol%). A mechanistic study revealed that transmetalation was a rate-determining step in the catalytic cycle, and also that the amide ligand on the zinc center played a key role in preparing reactive allylzinc species. Catalytic asymmetric allylations were also investigated, and high enantioselectivities were obtained using chiral diamine ligands. Copyright

Facile preparation of allylzinc species from allylboronates and zinc amide via a boron-to-zinc exchange process and their reactions with carbonyl compounds, imines and hydrazones

Facile formation of allylzinc species from allylboronate and zinc amide was discovered. The boron-to-zinc exchange process occurred smoothly to afford the corresponding allylzinc amides, which were successfully employed in catalytic allylation reactions with electrophiles. Asymmetric catalysis using a chiral zinc amide is also reported.

Mesoporous aluminosilicate-catalyzed allylation of carbonyl compounds and acetals

A mesoporous aluminosilicate (Al-MCM-41) was found to be an effective heterogeneous catalyst for the reaction of both carbonyl compounds and acetals with allylsilanes to afford the corresponding homoallyl silyl ethers and homoallyl alkyl ethers, respectively. Both the mesoporous structure and the presence of aluminum moiety were indispensable for the high catalytic activity of Al-MCM-41. Moreover, Al-MCM-41 could catalyze the reaction of acetals chemoselectively in the presence of the corresponding carbonyl compounds. The solid acid catalyst Al-MCM-41 could be recovered easily by filtration and could be reused three times without a significant loss of catalytic activity.