101655-05-4

Upstream product

• 67-56-1 methanol 
• 3516-64-1 Methyl-<γ-brom-β-phenyl-crotonat> 
• 5927-18-4 trimethyl phosphonoacetate 
• 4079-52-1 methoxymethyl phenyl ketone 
• 69511-47-3 methyl 4-methoxybut-2-ynoate 
• 98-80-6 phenylboronic acid 
• 5123-13-7 5,5-dimethyl-2-phenyl-1,3,2-dioxaborinane 
• 3461-50-5 methyl trans-3-methylcinnamate 

Downstream Products

• 99865-35-7 γ-Methoxy-β-phenyl-crotonsaeure vom F:54grad 

Relevant academic research and scientific papers

Dramatic Effect of γ-Heteroatom Dienolate Substituents on Counterion Assisted Asymmetric Anionic Amino-Cope Reaction Cascades

We report a dramatic effect on product outcomes of the lithium ion enabled amino-Cope-like anionic asymmetric cascade when different γ-dienolate heteroatom substituents are employed. For dienolates with azide, thiomethyl, and trifluoromethylthiol substituents, a Mannich/amino-Cope/cyclization cascade ensues to form chiral cyclohexenone products with two new stereocenters in an anti-relationship. For fluoride-substituted nucleophiles, a Mannich/amino-Cope cascade proceeds to afford chiral acyclic products with two new stereocenters in a syn-relationship. Bromide- and chloride-substituted nucleophiles appear to proceed via the same pathway as the fluoride albeit with the added twist of a 3-exo-trig cyclization to yield chiral cyclopropane products with three stereocenters. When this same class of nucleophiles is substituted with a γ-nitro group, the Mannich-initiated cascade is now diverted to a β-lactam product instead of the amino-Cope pathway. These anionic asymmetric cascades are solvent- and counterion-dependent, with a lithium counterion being essential in combination with etheral solvents such as MTBE and CPME. By altering the geometry of the imine double bond from E to Z, the configurations at the R1 and X stereocenters are flipped. Mechanistic, computational, substituent, and counterion studies suggest that these cascades proceed via a common Mannich-product intermediate, which then proceeds via either a chair (X = N3, SMe, or SCF3) or boat-like (X = F, Cl, or Br) transition state to afford amino-Cope-like products or β-lactam in the case of X = NO2.

Synthesis of 4-aryl-substituted butenolides and pentenolides by copper-catalyzed hydroarylation

We have investigated the effect of the type of protecting group used and the tether length of 4- and 5-hydroxy-substituted 2-alkynoates on the yields and selectivity of the product of hydroarylation. The use of methyl, methoxymethyl, and tert-butyldimethy