65755-82-0

Upstream product

• 556-82-1 3-methyl-2-buten-1-ol 
• 99309-29-2 (3-methyl-but-2-enyloxy)acetic acid 
• 591-51-5 phenyllithium 
• 170502-95-1 2-(3-methyl-but-2-enyloxy)-N-methoxy-N-methyl-acetamide 
• 3282-32-4 2-diazo-acetophenone 

Downstream Products

• 65755-94-4 3,3-dimethyl-2-phenyl-2-(trimethylsiloxy)-4-pentenal 
• 62894-04-6 phenyl prenyl ketone 
• 79164-15-1 3,3-dimethyl-2-phenyl-pent-4-enal 
• 65755-93-3 5-methyl-2-phenyl-2-(trimethylsiloxy)-4-hexenal 

Relevant academic research and scientific papers

Synthesis of alkynyl ethers and low-temperature sigmatropic rearrangement of allyl and benzyl alkynyl ethers

(Chemical Equation Presented) α-Alkoxy ketones 3 can be transformed into 1-alkynyl ethers 5 by a two-step procedure involving formation of the enol triflate or phosphate and base-induced elimination. Performing the same reaction sequence with allylic alcohols (R2OH, R2 = allyl) furnishes instead γ,δ-unsaturated carboxylic acid derivatives 6, derived from [3,3]-sigmatropic rearrangement of the intermediate allyl alkynyl ethers at -78 °C and trapping of the subsequently formed ketene with nucleophiles (Nu-H). Benzyl alkynyl ether 5 (R2 = benzyl) rearranges to indanone 7 upon heating to 60 °C.

Non-carbonyl-stabilized metallocarbenoids in synthesis: The development of a tandem rhodium-catalyzed bamford-stevens/thermal aliphatic claisen rearrangement sequence

A tandem rhodium-catalyzed Bamford-Stevens/Claisen rearrangement is presented. The tandem reaction uses Eschenmoser hydrazones for the in situ generation of non-carbonyl-stabilized diazo alkanes, which are presumably intercepted by Rh(II) catalysts to induce a 1,2-hydride migration. This sequence provides high levels of stereocontrol for the generation of simple acyclic (Z)-enol ethers. These enol ethers undergo either thermal or Lewis acid accelerated Claisen rearrangements to provide products of high diastereopurity. Also presented are cascade reactions, wherein a third chemical step occurs after the initial tandem sequence (i.e., Bamford-Stevens/Claisen/ene and Bamford-Stevens/Claisen/Cope). Copyright

Regiospecific Synthesis of β, γ-Unsaturated Ketones from Allylic Alcohols. Claisen Rearrangement of α-Allyloxy Ketone Enol Derivatives

β,γ-Unsaturated ketones are prepared with regiospecific C-C bond formation at the former γ-position of primary, secondary, or tertiary allylic alcohol precursors by a process involving sigmatropic Claisen rearrangement of intermediate α-allyloxy ket