24730-93-6

Upstream product

• 24730-94-7 ethyl 1-methyl-2,4-dioxocyclohexane-1-carboxylate 
• 52466-50-9 ethyl 4-ethoxy-2-oxocyclohex-3-ene-1-carboxylate 
• 1367352-54-2 C₁₆H₂₆N₂O 

Downstream Products

• 24730-90-3 4-(hydroxymethyl)-4-methylcyclohexanone 
• 54710-14-4 4-Dimethoxymethyl-4-methyl-cyclohex-2-enon 
• 54125-08-5 4-methyl-4-formylcyclohex-2-enone 

Relevant academic research and scientific papers

Experimental studies on the selective β-c-h halogenation of enones

Here we describe the realization of a one-pot protocol for the β-C-H halogenation of cyclic enones via umpolung of the β-carbon. The developed method includes hydrazone formation and selective β-halogenation (bromination, chlorination) with N-bromosuccini

Scalable synthesis of highly reactive 1,3-diamino dienes from vinamidinium salts and their use in Diels-Alder reactions

A practical and chromatography-free synthesis of vinamidinium salts and their use as diene precursors in Diels-Alder reactions is reported. Additionally, 1,3-dipyrrolidino-1,3-butadiene was shown to be significantly more reactive than Rawal's diene in a c

Lewis acid catalyzed procedure for selective conversion of the carbocyclic Diels-Alder adducts of Danishefsky's diene to 2-cyclohexenones and its extension to their one-pot syntheses

Conversion of the carbocyclic Diels-Alder adducts of 4-methoxy-2-trimethylsiloxy-1,3-butadiene (Danishefsky's diene), prepared by heating, to the corresponding 2-cyclohexenones was performed cleanly by use of Lewis acids such as Yb(OTf)3 and Bu

Racemic and asymmetric Diels-Alder reactions of 1-(2-oxazolidinon-3-yl)-3-siloxy-1,3-butadienes

Achiral and chiral 1-(2-oxazolidinon-3-yl)-3-siloxy-1,3-butadienes were prepared from readily available starting materials. Although more stable than the parent 1-amino-3-siloxy dienes, the 1-(2-oxazolidinon-3-yl)-3-siloxy-1,3-butadienes are still very reactive in Diels-Alder reactions, somewhat more than 1,3-dialkoxy-1,3-butadienes (e.g., Danishefsky's diene). The cycloadditions of the achiral and chiral dienes with several different dienophiles were examined. The reactions proceeded in good yield, with modest to high endo selectivity. The chiral dienes exhibited excellent facial selectivity in cycloadditions with α-substituted acroleins, maleic anhydride and N-phenylmaleimide. Upon reduction and hydrolysis of the cycloadducts, substituted cyclohexenones were obtained with ee's ranging from 22% to >98%.

1-amino-3-siloxy-1,3-butadienes: Highly reactive dienes for the Diels- Alder reaction

1-Amino-3-siloxy-1,3-butadienes represent a novel class of heteroatom- containing dienes with several useful properties. These dienes can be prepared efficiently by deprotonation of readily available vinylogous amides with potassium hexamethylsilazide, followed by silylation of the corresponding potassium enolates. This protocol has been found to be quite general for the preparation of various dienes containing different silyl and amino groups. Amino siloxy dienes readily undergo [4 + 2] cycloadditions with a wide range of electron-deficient dienophiles. The reactions generally occur under very mild conditions to afford the corresponding [4 + 2] adducts in high yields and with complete regioselectivity. High endo selectivity is observed in the case of N-phenylmaleimide and methacrolein. Other cycloadducts are usually obtained as mixtures of endo/exo diastereomers. The cycloadducts are versatile synthetic intermediates. They can be subjected to deprotonation, reduction, and Wittig olefination without any hydrolysis or elimination. In addition, the elimination of the amino group can be cleanly accomplished under acidic conditions leading to the formation of enones. A variety of substituted cyclohexenones can be prepared by this procedure.