57403-76-6

Upstream product

• 693-03-8 n-butyl magnesium bromide 
• 65092-79-7 (2R)-6-(Z)-benzylidene-3c,4-dimethyl-2r-phenyl-[1,4]oxazepane-5,7-dione 
• 109-72-8 n-butyllithium 
• 57403-84-6 4r-methoxymethyl-5t-phenyl-2-trans-styryl-4,5-dihydro-oxazole 
• 98314-62-6 (S,E)-1-(2-(hydroxymethyl)pyrrolidin-1-yl)-3-phenylprop-2-en-1-one 
• 107173-65-9 N-(3-phenylpropenoyl)-L-proline 
• 105526-93-0 (5S)-N-[(3S)-phenylheptanoyl]-5-triphenylmethoxymethyl-2-pyrrolidinone 
• 137542-83-7 (S)-4-tert-Butyl-2-((R)-2-phenyl-hexyl)-4,5-dihydro-oxazole 
• 120454-70-8 2-((R)-1-Carboxymethyl-pentyl)-benzoic acid 
• 142559-22-6 (R)-3-Phenyl-heptanoic acid benzyl-((R)-1-hydroxymethyl-propyl)-amide 
• 169870-67-1 (5S,6R,7R,12S,3'R,3R)-5,12-Bis(3-phenylheptanoyloxy)-1,8,13,16-tetraoxadispiro<5.0.5.4>hexadecane 
• 147666-53-3 Methyl-((R)-3-phenyl-heptanoyl)-carbamic acid tert-butyl ester 

Relevant academic research and scientific papers

Asymmetric conjugate additions to chiral α,β-unsaturated oxazolines with sulfonyl carbanions

Addition of sulfonyl carbanions with or without an electrophilic tether has been shown, under certain conditions, to add to α,β-unsaturated oxazolines in good yields and high de's. When 4-bromobutylsulfonyl carbanions are added to unsaturated oxazolines,

The 1,4-addition of organometallic reagents to enoates derived from pinanediol

The complex-induced, proximity effect-promoted 1,4-addition of RCu·BF3 and R2CuLi to enoates derived from (-)-pinanediol leads to adducts with the opposite sense of chirality (up to 98% d.e.).

Rhodium-catalyzed asymmetric 1,4-addition of arylboron reagents to α,β-unsaturated esters

Reaction of arylboron reagents, arylboronic acids or arylborates, which are readily accessible by lithiation of aryl bromides followed by treatment with trimethoxyborane, with α,β-unsaturated esters in the presence of rhodium/(S)-binap catalyst proceeded with high enantioselectivity to give high yields of optically active β-aryl esters of up to 98% ee. The enantioselectivity depends on the steric bulkiness of the ester moiety.

Synthetic applications of the β-lithiation of β-Aryl secondary amides: Diastereoselective and enantioselective substitutions

The sequence of β-lithiation and electrophilic substitution of β-aryl secondary amides is reported. The lithiations occur regioselectively at the β-position, and the resulting lithiated intermediates can be reacted with a wide range of electrophiles to give substituted products. Reactions of β-lithiated amides bearing an α-substituent provide substituted products with high diastereoselectivity. Electrophilic substitutions of β-lithiated N-methylamides in the presence of the chiral diamine (-)-sparteine provide highly enantioenriched products. The methodology is used to synthesize enantioenriched β-aryl β-substituted amides, acids, and lactones.

Diastereoselectivity in Iodotrimethylsilane-promoted Conjugate Additions of Organocopper Reagents to Chiral α,β-Unsaturated Imides and Amides

Conjugate additions of MeCu, PhCu and BuCu to the chiral enoylimides 2 a-c in the presence of iodotrimethylsilane and lithium iodide in THF give the adducts, 4a-c in yields above 90percent and diastereoselectivities from 80 to 93percent.The dominating diastereomers are different from those formed with LiR2Cu/TMSCl or in copper(I)-mediated addition of Grignard reagents.Corresponding additions to enoyl-amides of O-tritylprolinol also give high yields of conjugate adducts, but lower diastereoselectivities, with dominating configuration in the acyl part opposite to those from the imides.

Dispiroketals in synthesis (Part 16): Functionalised dispiroketals as new chiral auxiliaries; the synthesis of dihydroxylated dispiroketals in optically pure form and their application as bifunctional , C2-symmetrical, chiral auxiliaries for highly stereoselective Michael additions

A range of rigid, architecturally complex diols derived from dispiroketals have been synthesised.A bifunctional, C2-symmetrical, chiral auxiliary derived from these dihydroxylated dispiroketals has been used to induce a high degree of asymmetry in Michael additions of cuprates to a variety of di-α,β-unsaturated ester systems.

Dispiroketals in Synthesis (Part 14): Functionalised Dispiroketals as New Chiral Auxiliaries; Highly Stereoselective Michael Additions to a Bifunctional, C2-Symmetrical Chiral Auxiliary.

A bifunctional, C2-symmetrical chiral auxiliary derived from dihydroxylated dispiroketals has been used to induce a high degree of asymmetry in Michael additions of cuprates to a variety of di-α,β-unsaturated ester systems.

Regio-, Stereo-, and Enantioselectivity in the Electrophilic Reactions of 2-Amino-4-phenyl-3-butenenitriles

The allylic anion generated from 2-(N-methylanilino)-4-phenyl-3-butenenitrile (1) reacted with iodomethane and 3-bromo-1-chloropropane in THF/HMPA to give γ-substituted products exclusively, predominantly in the 2Z-configuration.Substitution of the N-methylanilino group with the methyl ether of L-(-)-ephedrine resulted in the generation of chiral aminonitrile 2.Lithiated 2 reacted sluggishly in THF with allyl bromide and benzyl chloride in the absence of HMPA to give the γ-substituted products predominantly in the 2Z-configuration, with little diastereoselectivity.The aminonitrile 3 prepared from cinnamaldehyde, L-(-)-ephedrine, and KCN was lithiated with 2 equiv of LDA resulting in high facial selectivity (76 - 100 percent diastereomeric excess) in alkylations in the presence of HMPA and LiI.Lithiated 3 reacted with propionaldehyde, benzaldehyde, and p-bromobenzaldehyde at -78 deg C to give the γ-addition products, predominantly in the 4R-configuration (64 -78 percent de).The stereochemistry of the isomers of each product was determined by chemical correlation and spectral methods including analyses of the CD spectra and X-ray diffraction.A bicyclic transition state C wherein lithium is chelated by both amino and alkoxy groups is proposed to interpret the observed stereoselectivity.