147599-27-7

Upstream product

• 4362-01-0 3-phenyl-2-hexenoic acid 
• 2313-01-1 5-ethyl-2(3H)-furanone 
• 98-80-6 phenylboronic acid 
• 147599-20-0 (2E,4R,5R)-5-hydroxy-2--4-phenyl-2-heptenenitrile 
• 147599-17-5 (2Z,4R,5R)-5-hydroxy-2--4-phenyl-2-heptenenitrile 
• 69178-10-5 2-styryl-1,3-dithiane 
• 5703-54-8 3-phenyl-hex-3-enoic acid 

Downstream Products

• 147471-46-3 Methanesulfonic acid (1R,2R)-1-ethyl-4-methanesulfonyloxy-2-phenyl-butyl ester 
• 35216-62-7 (S)-3-phenylhexane 
• 147471-45-2 (3R,4R)-3-Phenyl-hexane-1,4-diol 

Relevant academic research and scientific papers

Stereoconvergent Conjugate Addition of Arylboronic Acids to α-Angelica Lactone Derivatives: Synthesis of Stereochemically Complex γ-Butyrolactones

Catalyzed stereoconvergent 1,4-additions to unsaturated carbonyls are rare but of high potential value. This letter details the development of enantioselective arylation reactions of boronic acids and β,γ-butenolides. These reactions are catalyzed by commercially available hydroxy[(S)-BINAP]-rhodium(I) dimer to afford stereochemically complex γ-butyrolactone derivatives. The reaction products provide functionality amenable to further manipulation and can lead to products with up to three contiguous stereocenters. The reaction proceeds under a dynamic kinetic resolution manifold by isomerizing the achiral starting material into an interconverting mixture of enantiomeric conjugate acceptors, followed by catalyst-controlled, enantiomer-selective 1,4-addition. Base-promoted racemization of the intermediate α,β-butenolide is possible due to the high kinetic and thermodynamic acidity of the γ-proton.

Synthesis of versatile chiral intermediates by enantioselective conjugate addition of alkenyl Grignard reagents to enamides deriving from (R)-(-)- or (S)-(+)-2-aminobutan-1-ol

Conjugate addition of but-3-enylmagnesium bromide to the chiral crotonamide (R)-(+)- and (S)-(-)-3, followed by hydrolysis and oxidation, afforded enantiopure (R)-(+)- and (S)-(-)-3-methyladipic acids 8, respectively. Conjugate addition of vinylmagnesium chloride to the chiral crotonamide and cinnamamides (R)-(+)-3-5, followed by hydrolysis, gave the alkenoic acids (S)-12-14, respectively. Iodolactonization of the latter led to the 5-iodomethyllactones (+)-15-17, which were reduced by means of n- Bu3SnH into the trans-disubstituted 5-methyllactones (+)-19-21, respectively. Treatment of the iodomethyllactone (+)-16 with LiMe2Cu or n- Bu2CuLi furnished the trans-5-alkyl-4-phenyllactones (-)-22 or (+)-23.

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.

REACTION OF DITHIO-SUBSTITUTED CINNAMYLLITHIUM WITH CARBONYL COMPOUNDS: A TEST OF THE HSAB PRINCIPLE

By mediation of BF3.Et2O, dithio substituted cinnamyllithium 2 reacted predominantly at the α-site with carbonyl compounds.No selectivity was found when the reaction was performed in the absence of BF3.Et2O.