Abstractα-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 (R 2 OH, R 2 = 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 (R 2 = benzyl) rearranges to indanone 7 upon heating to 60 °C.Electron-rich alkynes, such as ynamines and ynol ethers, are functional groups that possess significant potential in organic chemistry for the formation of carbon-carbon bonds. 1 The synthetic utility of ynamides has been considerably expanded recently, along with the development of new methods for their facile preparation from simple building blocks. 2 1-Alkynyl ethers, while possessing many of the reactivity features of ynamides, have been far less investigated due to the relatively few methods currently available for their synthesis. 3 In this letter we present a mild and efficient method for the synthesis of diverse 1-alkynyl ethers and demonstrate that a facile sigmatropic rearrangement of allyl and benzyl alkynyl ethers furnishes products containing new carbon-carbon bonds.We have previously shown that treatment of allyl-1,1-dichlorovinyl ethers with 2.2 equiv of n-butyllithium at −78 °C, followed by quenching of the reaction mixture with excess alcohol, leads to rearranged γ,δ-unsaturated esters in high yield. 4 The reaction possesses many of the characteristics of a sigmatropic process, both in terms of its stereospecificity and geometrical requirements. We have proposed that an initially generated allyl alkynyl ether intermediate undergoes a [3,3]-sigmatropic rearrangement either as a neutral or as a negatively charged species.Due to its reactivity toward a range of functional groups, the use of the nucleophilic base nBuLi to generate the key intermediate in this reaction may be viewed as a potential limitation. Furthermore, the preparation of the allyl-1,1-dichlorovinyl ether substrate via methylenation of an allylic formate ester requires the use of toxic carbon tetrachloride in combination with triphenylphosphine. Since terminal and internal alkynes have been previously prepared from ketones by treatment of the corresponding enol phosphates or triflates with a non-nucleophilic base, 5 we sought to investigate the preparation of 1-alkynyl ethers from α-alkoxy ketones via E2 elimination of the derived enol triflates or phosphates.Following the procedure of Muthusamy et. al., 6 treatment of a toluene solution of diazoacetophenone 1a and menthol with a catalytic amount (10 mol %) of indium triflate at room temperature furnished α-alkoxy ketone 3a in 91% yield (Scheme 1). Formation of the enol triflate was achieved by stirring 3a with LiHMDS at −78 °C for one hour, followed by quenching with PhNTf 2 in DMPU/THF (1:2) and warming to room ...

Substituted benzyl alkynyl ethers, prepared from the corresponding α-alkoxy ketones in a two-step sequence involving enol triflate formation and KOtBu-induced E2 elimination, undergo [3,3]-sigmatropic rearrangement/intramolecular 5-exo-dig cyclization at 60°C to form substituted 2-indanones in good overall yields. 1,3-cis-disubstituted-2-indanones are formed preferentially when the benzylic substituent R1 is bulky. Substituted indenes may be prepared from 2-indanones in high yields by Horner-Wadsworth-Emmons reaction.

3,3]-Sigmatropic Rearrangement/5-exo-dig Cyclization Reactions of Benzyl Alkynyl Ethers: Synthesis of Substituted 2-Indanones and Indenes. -At 60°C, a number of substrates affords indanones like (III). Starting from ethers bearing bulky benzylic substituents, selective formation of cis-substituted indanones takes place. The indanones can be converted into indene derivatives. -(TUDJARIAN, A. A.; MINEHAN*, T. G.; J. Org. Chem. 76 (2011) 9, 3576-3581, http://dx.

In an extension of our studies on low-temperature rearrangements of 1-alkynyl ethers, we describe herein the [3,3]-sigmatropic rearrangement of in situ formed propargyl alkynyl ethers to allenyl ketenes, which furnish...

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