15250-29-0

Upstream product

• 2327-99-3 1-phenylpropadiene 
• 100-52-7 benzaldehyde 
• 7042-34-4 ethyl c-α–methylcinnamate 
• 7042-33-3 ethyl (E)-2-methyl-3-phenyl-2-propenoate 
• 673-32-5 1-Phenylprop-1-yne 
• 124-38-9 carbon dioxide 
• 680195-78-2 ethyl (E)-3-phenyl-2-(trimethylsilylmethyl)prop-2-enoate 
• 100-34-5 benzene diazonium chloride 
• 1895-97-2 2-methyl-3-phenylacrylic acid 

Downstream Products

• 1536472-67-9 (±)-1,1′-binaphthyl-2-2′-diyl (Z)-2-methyl-3-phenyl-2-propenoate 
• 13099-50-8 2-methyl-1-phenyl-1-propene, β,β-dimethylstyrene 

Relevant academic research and scientific papers

Visible-Light-Driven alkyne hydro-/carbocarboxylation using CO2 via iridium/cobalt dual catalysis for divergent heterocycle synthesis

We present herein the first visible-light-driven hydrocarboxylation as well as carbocarboxylation of alkynes using CO2 via an iridium/cobalt dual catalysis. Such transformations provide access to various pharmaceutically important heterocycles in a one-pot procedure from readily available alkynes. Coumarins, 2-quinolones, and 2-benzoxepinones were directly accessed through a one-pot alkyne hydrocarboxylation/alkene isomerization/cyclization sequence in which the Ir photocatalyst serves a dual role to promote single-electron transfer in alkyne hydrocarboxylation and energy transfer in the subsequent alkene isomerization. Moreover, an unprecedented cobalt carboxylation/acyl migration cascade enables alkyne difunctionalization to introduce γ-hydroxybutenolides with high efficiency. We expect that this cascade strategy will inspire new perspectives for alkyne and alkene difunctionalization.

Key structural features of cis-cinnamic acid as an allelochemical

1-O-cis-cinnamoyl-β-d-glucopyranose is one of the most potent allelochemicals isolated from Spiraea thunbergii Sieb. It is suggested that it derives its strong inhibitory activity from cis-cinnamic acid, which is crucial for phytotoxicity. It was synthesized to confirm its structure and bioactivity, and also a series of cis-cinnamic acid analogues were prepared to elucidate the key features of cis-cinnamic acid for lettuce root growth inhibition. The cis-cyclopropyl analogue showed potent inhibitory activity while the saturated and alkyne analogues proved to be inactive, demonstrating the importance of the cis-double bond. Moreover, the aromatic ring could not be replaced with a saturated ring. However, the 1,3-dienylcyclohexene analogue showed strong activity. These results suggest that the geometry of the C-C double bond between the carboxyl group and the aromatic ring is essential for potent inhibitory activity. In addition, using several light sources, the photostability of the cinnamic acid derivatives and the role of the C-C double bond were also investigated.

Correlation of hydrolysis and desilylation of 2-[(trimethylsilyl)methyl] acrylate derivatives in aqueous alkali solutions

Hydrolysis and desilylation reaction of 2-[(trimethylsilyl)methyl]acrylate (=2-[(trimethylsilyl)methyl] prop-2-enoate) derivatives were studied to evaluate the effect of the presence/absence of a further conjugating substituent (Schemes 3 and 4 and Tables 1 and 2). The substrates having a nonconjugating substituent at the acrylate moiety were stable to dilute alkali conditions, and afforded simple hydrolysis products under concentrated alkali conditions. In contrast, both hydrolysis and desilylation occurred from the substrates bearing conjugated substituents at the acrylate skeleton. The difference in reactivity can be explained in terms of the stabilization of the intermediate anion.

Tungsten(0) alkylidene complexes stabilized as pyridinium ylides: New aspects of their synthesis and reactivity

The interaction of dihydropyridines with alkoxycarbene complexes of tungsten has been shown to lead to pyridinium ylid complexes: this transformation has now been applied to the synthesis of a hydroxyl-containing ylid complex by ring-opening of the pentacarbonyl (2-oxacyclopentylidene) tungsten(0) complex and to the synthesis of a series of chiral ylid complexes both from chiral and non-chiral carbene complexes by the use of dihydropyridines and dihydronicotines, respectively. The transfer of the alkylidene moiety of these complexes to nucleophilic olefins will be outlined and discussed. Especially relevant is the interaction of these pyridinium ylid complexes with unsaturated substrates such as dihydropyridines, enamines, and β-alkoxy bis(trimethyl-silyl) ketene acetals. This latter reaction leads to conjugated carboxylic acids, and has been be applied to a new synthesis of a honey bee pheromone, the queen substance.

Organic Syntheses via Transition Metal Complexes, 19. - β-Methylenecyclopentenones via Iron Carbonyl-Induced Cycloaddition of Alkynes to Allenes and Carbon Monoxide

From alkynes, allenes, and carbon monoxide β-methylenecyclopentenones 3 and 4 are obtained in a one-pot procedure.The reaction involves a template-induced cycloaddition via carbonyl iron complexes as intermediates.The regio- and stereoselectivity of this synthesis has been studied by means of model reactions.The fragmentation pattern observed in the mass spectrum of these compounds corresponds to the retro-synthesis.