74603-51-3

Upstream product

• 767-99-7 2-phenylbut-2-ene 
• 344355-75-5 (E)-5-Hydroxy-4-methyl-5-phenyl-2-piperidin-1-yl-hex-2-enenitrile 
• 623-43-8 crotonic acid methyl ester 
• 98-86-2 acetophenone 
• 87143-55-3 (2R,3R)-5-Methoxy-2,3-dimethyl-2-phenyl-tetrahydro-furan 
• 106501-28-4 (2R,3R)-4-[1,3]Dithian-2-ylidene-3-methyl-2-phenyl-butan-2-ol 
• 106501-28-4 (2R,3S)-4-[1,3]Dithian-2-ylidene-3-methyl-2-phenyl-butan-2-ol 
• 87143-46-2 Diisopropyl-carbamic acid (Z)-(3S,4R)-4-hydroxy-3-methyl-oct-1-enyl ester 

Relevant academic research and scientific papers

Electroreductive coupling of aromatic ketones, aldehydes, and aldimines with α,β-unsaturated esters: Synthesis of 5-aryl substituted γ-butyrolactones and lactams

The electroreductive intermolecular coupling of aromatic ketones and aldehydes with α,β-unsaturated esters in the presence of TMSCl gave the adducts as γ-trimethylsiloxy esters. The detrimethylsilylation of the adducts with TBAF afforded 5-aryl substituted γ-butyrolactones. The electroreductive coupling of N-(4-methoxyphenyl)-1-arylmethaneimines with methyl acrylate in the presence of TMSCl gave the adducts as methyl 4-aryl-4-((4-methoxyphenyl)amino)butanoates. The adducts were transformed to 5-aryl-γ-butyrolactams by cyclization with NaH and subsequent oxidation with CAN. (±)-Norcotinine was prepared from nicotinaldehyde by this method. The electroreductive coupling of aromatic ketones and aldimines with acrylonitrile in the presence of TMSCl gave 4-aryl-4-(trimethylsiloxy)butanenitriles and 4-aryl-4-((4-methoxyphenyl)amino)butanenitriles, respectively.

Unexpected TiIII/Mn-promoted pinacol coupling of ketones

Titanocene(III) chemistry has emerged in the last decades as an indispensable tool in C-C bond-forming reactions. In this context, pinacol and related reactions allow the stereoselective synthesis of vicinal diols. In this work, we present new applications of these reactions using as starting materials aromatic ketones. Simple and smooth reaction conditions have been developed and have been applied for inter- and intramolecular processes. We also describe that although Cp2TiCl is usually used as a monoelectronic reducing agent, it can be also used as an efficient Lewis acid.

Dichotomous Regiochemistry of Aldehyde and Ketone in the Reaction with Dithio-Substituted Crotyllithium

The crotyllithium compound 1 generated from (E)-2-(1-propen-1-yl)-1,3-dithiane reacted with an aldehyde to give γ-products in favor of the anti isomer.This regio- and diastereoselective reaction is applicable to syntheses of trans β,γ-disubstituted γ-lactones, including natural products of (+/-)-eldanolide and (+/-)-trans quercus lactone.The γ(1,2)-adducts obtained from the reaction of 1 and enals underwent alkoxy-Cope rearrangements on treatment with KH.The consequence is virtually complete α(1,4)-addition of crotyllithium 1 to α,β-unsaturated aldehydes.Crotyllithium 1 reacted with ketones at either the α- or the γ-site, depending on the nature of respective ketone.The regiochemistry is well interpreted by the hard and soft acids and bases principle, when the steric effect is a minor controlling factor.The effects of HMPA and reaction temperature on the regioselectivity were also evaluated.

HIGHLY DIASTEREOSELECTIVE SYNTHESIS OF DI-AND TRISUBSTITUTED 4-BUTANOLIDES FROM ALDEHYDES AND KETONES VIA THREE-CARBON-EXTENSION BY ALLYLIC HOMOENOLATE REAGENTS

Lithiated or titanated O-allyl carbamates 7 or 8 add to aldehydes and ketones regio- and diastereoselectively to yield-O-(4-hydroxy-1-alkenyl)carbamates 9, which are converted to γ-lactones 12 with an one-pot procedure.

Three carbon annelation reagents: unsaturated alpha aminonitriles as homoenolate equivalents

α-Aminonitriles and (R = Me) can react as either acyl anion or β-homoenolate equivalents on varying the reaction conditions. Both modes of reaction are potentially useful in three carbon annelations.