80816-24-6

Upstream product

• 30649-18-4 β-hydroxystyrene 
• 109-92-2 ethyl vinyl ether 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 108-05-4 vinyl acetate 
• 109-53-5 isobutyl vinyl ether 
• 764-47-6 vinyl propyl ether 
• 176207-83-3 tert-Butyl-[2-iodo-1-((E)-3-phenyl-allyloxy)-ethoxy]-dimethyl-silane 

Downstream Products

• 137151-87-2 (S)-3-phenyl-4-pentenal 
• 60091-38-5 4-phenyl-5-hexen-2-ol 
• 173673-32-0 3,4-dihydro-2-methyl-3-phenyl-2H-pyrrole 
• 127826-97-5 N-(3-phenyl-4-pentylidene)-2-benzenesulfenamide 
• 127826-96-4 N-(3-phenyl-4-pentylidene)-2-benzothiazolesulfenamide 
• 53646-85-8 1,3-diphenyl-1H-pyrrole 
• 80816-30-4 3-phenyl-4-pentenol 
• 939-21-9 3-phenyl-4-pentenal 

Relevant academic research and scientific papers

Synthesis of 1,3- and 1,2,3-functionalized pyrroles via Ir(I)-catalyzed vinylation of allyl alcohols

[Figure not available: see fulltext.] An efficient method for the preparation of 1,3-disubstituted and 1,2,3-trisubstituted pyrroles was developed through a sequence involving O-vinylation of allyl alcohols followed by Claisen rearrangement and further ozonolysis, concurring in a Paal–Knorr reaction with primary amines. Hg(II) and Ir(I) catalysts and different vinylating reagents were tested. The best results were consistently obtained with the [Ir(cod)Cl]2–vinyl acetate system. The featured methodology gives access to functionalized pyrroles in overall good yields, whose chemical architecture may awake interest for assorted applications.

Palladium(II)-catalyzed asymmetric coupling of allylic alcohols and vinyl ethers: Insight into the palladium and copper bimetallic catalyst

The use of PdX2, CuX2 (X = OAc, OCOCF3, or Cl), and catechol together with (S,S)-4,4'-bisbenzyl- 2,2'-bioxazoline under O2 induces the asymmetric coupling of cinnamyl alcohols and vinyl ethers to give (R)-(+)-2-alkoxy-4-benzylidenetetrahydrofurans in 40-53% ee (79% yield). The present study provides implications for the so-called Wacker catalyst of PdX2 and CuX2, in terms of that the anionic ligands (X) of Pd and Cu interchange between two metals.

Highly regioselective [3,3] rearrangement of aliphatic allyl vinyl ethers catalyzed by a metalloporphyrin complex, Cr(TPP)Cl

The Claisen rearrangement of simple aliphatic allyl vinyl ethers catalyzed by a metalloporphyrin, Cr(TPP)Cl, is described. The porphyrin-based Lewis acid catalyst can effectively accelerate the rearrangement via a concerted [3,3] pathway with a minimal degree of bond ionization of the substrates, providing the corresponding Claisen products in moderate to high yields and almost perfect regioselectivity at low catalyst loading.

(2,7-Disubstituted-1,8-biphenylenedioxy)bis(dimethylaluminum) as Bidentate Organoaluminum Lewis Acids: Elucidation and Synthetic Utility of the Double Electrophilic Activation Phenomenon

A series of (2,7-disubstituted-1,8-biphenylenedioxy)bis(dimethylaluminum) (2) has been readily prepared in situ by treatment of the requisite 2,7-disubstituted-1,8-biphenylenediol (1) with Me3Al (2 equiv) in CH2Cl2 at room temperature; this primarily relies on the successful establishment of a new synthetic procedure of 1 starting from inexpensive m-anisidine. Evaluation of 2 as a bidentate organoaluminum Lewis acid has been performed by the reduction of ketonic substrates using Bu 3SnH as a hydride source in comparison to the conventional monodentate Lewis acid dimethylaluminum 2,6-xylenoxide (11), uncovering the significantly high activation ability of 2 toward carbonyl. Particularly, (2,7-dimethyl-1,8-biphenylenedioxy)-bis(dimethylaluminum) (2a) exerted the highest reactivity, which has also been emphasized in the Mukaiyama aldol reaction. The structure of the bidentate Lewis acid 2 was unambiguously determined by single-crystal X-ray diffraction analysis of 2g possessing a bulky 3,5-di-tert-butylphenyl substituent, revealing the rigid dimeric assembly in the solid state. The double electrophilic activation of carbonyl substrate by 2a has been supported by low-temperature 13C NMR analysis as well as theoretical study using the Gaussian 98 program. Moreover, unique stereoselectivity has been observed in the 2a-promoted Mukaiyama Michael addition, and highly chemoselective functionalization of carbonyl compounds in the presence of their acetal counterparts has been realized using 2a. Finally, the effectiveness of 2a for the activation of ether functionality has been demonstrated in the Claisen rearrangement of allyl vinyl ethers.

Iminyl Radicals: Part I. Generation and Intramolecular Capture by an Olefin.

Slow addition of tributylstannane to sulphenylimines 2 give the corresponding Δ1-pyrrolenines 5 by an intramolecular addition of the intermediate iminyl radical, a process which can be easily coupled to an intermolecular addition to an electrophilic olefin.

Enantioselective activation of ethers by chiral organoaluminum reagents: Application to asymmetric Claisen rearrangement

The asymmetric Claisen rearrangement of allyl vinyl ethers has been effected with a chiral organoaluminum reagent, (R)-1 or (S)-1 as an example of the enantioselectie activation of ether substrates. This method provides a facile asymmetric synthesis of various acylsilanes and acylgermanes with high optical purity. Among various trialkylsilyl substituents of chiral organoaluminum reagent 1, use of the more bulky t-butyldiphenylsilyl group exhibits the highest enantioselectivity. The conformational analysis of two possible chairlike transition-state structures of an allyl vinyl ether substrate reveals that a chiral organoaluminum reagent 1 can discriminate between these two conformations only by a difference in the orientation of α-methylene groups of ethers.

ALIPHATIC CLAISEN REARRANGEMENT PROMOTED BY ORGANOALUMINIUM REAGENTS.

Organoaluminium compounds, R//3Al, promote the Claisen rearrangement of allyl vinyl ether derivatives at room temperature under transfer of R or H as a nucleophile to the aldehydic carbon. Treatment of 1-butyl-2-propenyl vinyl ether with a hexane solution of Me//3Al (1. 0 M, 2. 2 equiv) in CH//2ClCH//2Cl at 25 degree C afforded 5-decen-2-ol (91% yield, E/Z equals 47/53), which was produced by the left bracket 3,3 right bracket sigmatropic rearrangement and successive methylation. The rearrangements with alkynylation, alkenylation, and hydrogenation are also achieved. The regular Claisen rearrangement products, of gamma , delta -unsaturated aldehydes (ketones), are obtained at 25 degree C in good to excellent yields with Et//2AlSPh (2. 5 equiv) or the combination of Et//2AlCl (2. 0 euiv) and PPh//3 (2. 2 equiv).