694457-23-3

Upstream product

• 4028-23-3 Allylchlorodimethylsilane 
• 119-56-2 (4-chlorophenyl)phenylmethanol 
• 258277-20-2 N-tosyl-[(4-chlorophenyl)(phenyl)methyl]amine 
• 762-72-1 allyl-trimethyl-silane 
• 831-81-2 4-chlorophenyl(phenyl)methane 
• 70122-89-3 tert-butyl allyl carbonate 

Downstream Products

• 1628714-01-1 (Z)-1-chloro-4-(1-phenylbut-2-enyl)benzene 
• 1628714-00-0 (E)-1-chloro-4-(1-phenylbut-2-enyl)benzene 

Relevant academic research and scientific papers

Direct Dehydroxylative Coupling Reaction of Alcohols with Organosilanes through Si-X Bond Activation by Halogen Bonding

The combined use of a halogen bond (XB) donor with trimethylsilyl halide was found to be an efficient cocatalytic system for the direct dehydroxylative coupling reaction of alcohol with various nucleophiles, such as allyltrimethylsilane and trimethylcyanide, to give the corresponding adduct in moderate to excellent yields. Detailed control experiments and mechanistic studies revealed that the XB interaction was crucial for the reaction. The application of this coupling reaction is also described.

A general Br?nsted acid-catalyzed allylation of benzhydryl alcohols

Efficient Br?nsted acid-catalyzed allylation of benzhydryl alcohols has been developed. The reaction occurs within 5?min in the presence of sub-stoichiometric amounts of HBF4·OEt2to afford the desired products in good to excellent yields. A variety of functional groups were tolerated under the developed conditions including amides, aldehydes, hydroxyl and carboxylic acid.

Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights

Palladium-catalyzed allylic substitution reactions are among the most efficient methods to construct C-C bonds between sp3-hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a "soft"-nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with "hard" nucleophiles, which attack the metal before C-C bond formation. Introduced herein is a rare nickel-based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft-nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising. Just a softy: Contrary to what would be predicted, organosodium nucleophiles derived from diarylmethane pronucleophiles are shown to behave as soft nucleophiles in nickel-catalyzed allylic substitution reactions. This general reaction is demonstrated to proceed through a double inversion pathway. A promising asymmetric version is presented.

Raising the p K a Limit of soft nucleophiles in palladium-catalyzed allylic substitutions: Application of diarylmethane pronucleophiles

The Tsuji-Trost allylic substitution reaction provides a useful and efficient approach to construct C-C bonds between sp3-hybridized carbons. The widely accepted paradigm for classifying the mode of attack of nucleophiles on palladium π-allyl intermediates in the Tsuji-Trost reaction is based on the pKa of the pronucleophile: (1) stabilized or soft carbon nucleophiles and heteroatom nucleophiles (e.g., pronucleophiles with pKa's a's > 25). One of the keys to the continuing development of allylic substitution processes remains broadening the scope of soft nucleophiles. Herein we report a general method for the room temperature Pd-catalyzed allylic substitution with diarylmethane derivatives (pKa's up to 32). The synthetic significance of the method is that it provides a rapid access to products containing allylated diarylmethyl motifs. The method is general for a wide range of nucleophiles derived from diarylmethanes and heterocyclic derivatives. A procedure for the Pd-catalyzed allylic substitutions to afford diallylation products with quaternary centers is also described. With triarylmethanes and alkylated diarylmethanes the corresponding allylated products are isolated. We anticipate that the described method will be a valuable complement to the existing arsenal of nucleophiles in Pd-catalyzed allylic substitutions. Mechanistic studies show that the nucleophile derived from diphenylmethane undergoes external attack on π-allyl palladium species under our reaction conditions. This unexpected observation indicates that diarylmethane derivatives behave as soft or stabilized nucleophiles. The results of this study indicate that the cutoff between soft and hard nucleophiles should be raised from a pronucleophile pK a of 25 to at least 32.

Catalytic coupling of N-benzylic sulfonamides with silylated nucleophiles at room temperature

In the presence of 2-10 mol% of Tf2NH, a range of N-benzylic sulfonamides smoothly react with allylic, propargylic, benzylic, or hydrido silanes at room temperature via sp3 carbon-nitrogen bond cleavage to afford structurally diverse products in moderate to excellent yields and with high chemo- and regioselectivity.

Efficient and mild iron-catalyzed direct allylation of benzyl alcohols and benzyl halides with allyltrimethylsilane

An efficient and mild iron-catalyzed direct allylation of benzyl alcohols and benzyl halides with allyltrimethylsilane has been developed. The present reaction would provide an excellent alternative to published methods because of its excellent yields, sustainable catalyst, and mild conditions. Copyright Taylor & Francis Group, LLC.

Direct allylation of α-aryl alcohols with allyltrimethylsilane catalyzed by heterogeneous tin ion-exchanged montmorillonite

The direct allylation of α-aryl alcohols with allyltrimethylsilane efficiently proceeded in the presence of tin ion-exchanged montmorillonite under mild conditions according to the proper addition order of reactants and a catalyst.

Boron trihalide mediated substitution of hydroxyl groups with alkenyl, alkynyl, and allyl moieties

The coupling of alcohols with alkenyl- and alkynylboron dihalides with high olefin stereoselectivity is described. The reaction provides a facile route to internal acetylenes. Notably, the allylation of propargylic alcohols mediated by boron trichloride p

Nucleophilic substitution reactions of alcohols with use of montmorillonite catalysts as solid Bronsted acids

(Chemical Equation Presented) We have developed an environmentally benign synthetic approach to nucleophilic substitution reactions of alcohols that minimizes or eliminates the formation of byproducts, resulting in a highly atom-efficient chemical process. Proton- and metal-exchanged montmorillonites (H- and Mn+-mont) were prepared easily by treating Na +-mont with an aqueous solution of hydrogen chloride or metal salt, respectively. The H-mont possessed outstanding catalytic activity for nucleophilic substitution reactions of a variety of alcohols with anilines, because the unique acidity of the H-mont catalyst effectively prevents the neutralization by the basic anilines. In addition, amides, indoles, 1,3-dicarbonyl compounds, and allylsilane act as nucleophiles for the H-mont-catalyzed substitutions of alcohols, which allowed efficient formation of various C-N and C-C bonds. The solid H-mont was reusable without any appreciable loss in its catalytic activity and selectivity. Especially, an Al3+-mont showed high catalytic activity for the α-benzylation of 1,3-dicarbonyl compounds with primary alcohols due to cooperative catalysis between a protonic acid site and a Lewis acidic Al3+ species in its interlayer spaces.

Generation of cations from alkoxides: Allylation of propargyl alcohols

The reaction of alkoxides with boron trichloride results in the generation of cations in the absence of Bronsted acids. The absence of a Bronsted acid can make a difference in subsequent transformations such as allylation reactions. Copyright