77118-87-7

Usage

Synthesis

To a solution of the bis-phosphoramide catalyst (59 mg, 0.1 mmol) in CH2Cl2 (1 mL) and diisopropylethylamine (1.0 mL) under N2 at ?78 °C was added allyltrichlorosilane (580 μL, 4.0 mmol). The solution was stirred at ?78 °C for 10 min before benzaldehyde (200 mL, 2.0 mmol) was added. The resulting mixture was stirred at this temperature for 8 h whereupon the cold solution was poured in to a mixture of saturated aqueous NaHCO3 (10 mL) and saturated aqueous KF (10 mL) at 0 °C with vigorous stirring. The mixture was stirred for 2 h at room temperature and then fifiltered through Celite. The layers were then separated and the aqueous layer was extracted with CH2Cl2 (3 × 30 mL). The combined organic extracts were dried (MgSO4), fifiltered, and concentrated. The oily residue was purifified by column chromatography (silica gel) eluting with CH2Cl2:pentane (3:1) followed by CH2Cl2 to give 254 mg (85%) of the benzylic alcohol in 87% ee. Reference: Denmark, S. E.; Fu, J. J. Am. Chem. Soc. 2001, 123, 9488?9489

Upstream product

• 6249-80-5 1-phenylbut-3-en-1-one 
• 99493-25-1 diisopropyl (R,R)-2-allyl-1,3,2-dioxaborolane-4,5-dicarboxylate 
• 17381-88-3 Diallyltin(IV) dibromide 
• 100-52-7 benzaldehyde 
• 1730-25-2 allylmagnesium bromide 
• 124821-92-7 d-B-allylbis(2-isocaranyl)borane 
• 2622-05-1 allylmagnesium bromide 
• 24850-33-7 allyltributylstanane 
• 99493-25-1 diisopropyl 2-allyl-1,3,2-dioxaborolane-4,5-dicarboxylate (tartrate allylboronate) 
• 18760-02-6 allyldiethylaluminium 
• 85116-38-7 (+)-diisopinocampheylallylborane 
• 95978-76-0 allyldiisobutylaluminium 
• 106-95-6 allyl bromide 
• 7785-70-8 2,6,6-trimethylbicyclo[3.1.1]hept-2-ene 

Downstream Products

• 22135-49-5 (S)-1-phenylbutan-1-ol 
• 96854-34-1 (S)-3-phenyl-1,3-propanediol 
• 183620-66-8 tert-butyl-dimethyl-(1-phenyl-but-3-enyloxy)-silane 
• 133271-05-3 (S)-3-hydroxy-3-phenyl-propionaldehyde 
• 100-52-7 benzaldehyde 
• 60340-28-5 (S)-1-phenyl-5-hexen-3-ol 
• 594836-75-6 (R)-phenyl 1-phenyl-3-butenyl ether 
• 491837-37-7 (1S)-2-((S)-oxiranyl)-1-phenylethanol 
• 757956-01-7 (1S)-2-((R)-oxiranyl)-1-phenylethanol 
• 5381-93-1 (4S)-4-hydroxy-4-phenylbutan-2-one 
• 913723-00-9 bromoacetic acid 1-phenylbut-3-enyl ester 
• 942154-15-6 C₁₅H₂₀O₃ 
• 942154-16-7 4-(iodomethyl)-6-phenyl-1,3-dioxan-2-one 
• 942154-17-8 (1S,3R)-3,4-epoxy-1-tert-butyldimethylsilyloxy-1-phenyl-butane 

Relevant academic research and scientific papers

Enantioselective Synthesis of Homo-allylic Alcohols from Chiral Allylic Tin(IV) (+)-Diethyl Tartrate Complexes and Aldehydes

A quite simple procedure to synthesize optically active secondary homoallylic alcohols from the reaction between aldehydes and allylic tin(IV) complexes containing (+)-diethyl tartrate as chiral auxiliary ligand is reported.

Application of a high-throughput enantiomeric excess optical assay involving a dynamic covalent assembly: parallel asymmetric allylation and ee sensing of homoallylic alcohols

Asymmetric Ir-catalyzed C-C coupling of primary alcohols with allyl-acetates, as described by Krische, to form chiral secondary homo-allylic alcohols were performed in parallel as a means to optimize the ee values thereof. Specifically, approximately 400 examples of this reaction were performed by varying the catalyst, added acids and bases, and starting reactants, to form 4-phenyl-1-butene-4-ol (1). The ee values for the transformations were determined in a high-throughput fashion using a 4-component assembly that creates a circular dichroism signal indicative of the extent of asymmetric induction. Further, a parallel and rapid quantitative TLC method measures the yield of each reaction, revealing which reactions give reliable ee values in the CD-based assay. Overall, the nearly 200 reactions whose ee values were determined could be quantitated in under two hours. Using a combination of the TLC method to measure yield with the CD-assay to measure ee values, several trends in reaction conditions were revealed. For example, it was found that the cyclometalated iridium catalyst modified by BINAP and m-nitro-p-cyano-benzoic acid delivered adduct 1 with the highest levels of enantiomeric enrichment (94%), whereas the corresponding SEGPHOS-modified catalyst gave a comparable yield but lower ee (91%). Most importantly, this study shows that supramolecular assemblies can report hundreds of ee values in a rapid and reliable fashion to analyze parallel synthesis routines.

An enantioselective allylation reaction of aldehydes in an aqueous medium

An enantioselective allylation reaction of aldehydes with enantioselectivities up to 92% has been achieved in an aqueous medium, by using (S,S)-2,6-bis(4-isopropyl-2-oxazolin-2-yl)pyridine as the chiral source.

Polystyrenes with chiral phosphoramide substituents as Lewis base catalysts for asymmetric addition of allyltrichlorosilane: Enhancement of catalytic performance by polymer effect

In the asymmetric addition of allyltrichlorosilane to benzaldehyde, polystyrenes with chiral phosphoramide substituents as Lewis base catalysts showed up to 2.4 times better catalytic activity and 1.4 times higher enantioselectivity than the corresponding

Synthesis of polysaccharide derivatives bearing pyridine N-oxide groups and their use as asymmetric organocatalysts

Novel amylose and cellulose derivatives bearing pyridine N-oxide groups were synthesized, and their performance as asymmetric organocatalysts was investigated. The amylose derivatives bearing 3-pyridyl N-oxide groups enantioselectively catalyzed the allyl

Synthesis of Enantiomerically Enriched Homoallylic Alcohols and of 1,2-dien-4-ols Using Chiral Tin(IV) Complexes Containing Diethyl Tartrate as an Auxiliary Ligand

Chiral allylic tin(IV) complexes 3 are prepared by treatment of tin dichloride with 2 equiv of doubly deprotonated diethyl tertrate followed by addition of an allylic bromide.The reaction of 3 with aldehydes affords optically active homoallylic alcohols in 50-80percent yield and in 40-60percent ee.When applied to propargyl bromide this procedure leads to optically active 1,2-dien-4-ols, and when 2-carbethoxyallyl bromide is used chiral γ-substituted α-methylene-γ-butyrolactones can be easily obtained.

Chiral sulfoxides in the enantioselective allylation of aldehydes with allyltrichlorosilane: A kinetic study

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Pd(II)-catalyzed intermolecular direct C-H bond iodination: An efficient approach toward the synthesis of axially chiral compounds via kinetic resolution

An efficient protocol to synthesize axially chiral compounds via kinetic resolution by Pd(II)-catalyzed direct C-H iodination was realized (up to s = 27). The iodide product could be easily transformed to aryl-substituted pyridine N-oxides via the Suzuki-

Enantioselective Allylation of Oxocarbenium Ions Catalyzed by Bi(OAc)3/Chiral Phosphoric Acid

Phthalides as the crucial core skeletons are found extensively in natural products and biological active molecules. Herein we disclose an asymmetric allylation of 3-hydroxyisobenzofuran-1(3H)-ones with boron allylation reagents to construct chiral phthali