Claisen rearrangements compounds

Compound 1, 2,2-diniethyl-4-pentenal, has been prepared by the Claisen rearrangement route described above and by reaction of isobutyraldehyde with allyl chloride in the presence of aqueous sodium hydroxide and a phase-transfer catalyst. Both routes are applicable to the synthesis of a variety of substituted 4-pentenals. 

Ether groups in the benzene ring of quinazoline behave as in ethers of homocyclic aromatic compounds, e.g., they can be demethylated with anhydrous aluminum chloride. Allyl ethers also undergo a Claisen rearrangement/ ... 

Ally lie ethers of enols (ally lie vinylic ethers) also undergo the Claisen rearrange-ment in fact, it was discovered with these compounds first ... 

The stereochemistry of Ireland-Claisen rearrangements of cyclic compounds is sometimes indicative of reaction through a boat TS. For example, the major product from 2-cyclohexenyl propanoate is formed through a boat TS.244... 

The Shikimate pathway is responsible for biosynthesis of aromatic amino acids in bacteria, fungi and plants [28], and the absence of this pathway in mammals makes it an interesting target for designing novel antibiotics, fungicides and herbicides. After the production of chorismate the pathway branches and, via specific internal pathways, the chorismate intermediate is converted to the three aromatic amino acids, in addition to a number of other aromatic compounds [29], The enzyme chorismate mutase (CM) is a key enzyme responsible for the Claisen rearrangement of chorismate to prephenate (Scheme 1-1), the first step in the branch that ultimately leads to production of tyrosine and phenylalanine. 

Scheme 2.196. 5-exo-dig-cyclization/Claisen rearrangement of compounds of type 2-877. 

Jasmonates are important odorant compounds. For the synthesis of new substances of this type, Giersch and Forris developed a domino Claisen/ene/retro-ene process which allows the acid-catalyzed transformation of sorbyl alcohol 4-285 and the cyclic acetals 4-286 into the cycloalkenone 4-292 with the proposed intermediates 4-287 to 4-291 (Scheme 4.61) [97]. A similar domino process had been described by Srikrishna and coworkers [98]. Acyclic acetals gave only the Claisen rearrangement products. 

A solvent-free synthesis of benzo[b]furan derivatives 10-79, a class of compounds which is often found in physiologically active natural products, was described by Shanthan Rao and coworkers. These authors heated phosphorane 10-71 for 8 min in a microwave oven and obtained the benzo[b]furan 10-74 in 73% yield (Scheme 10.18) [25]. The sequence is initiated by an intramolecular Wittig reaction, providing alkyne 10-72 this underwent a subsequent Claisen rearrangement to give the intermediate 10-73. Also in this case, normal oil-bath heating gave much lower yields (5%) of the desired product the authors hypothesize that the micro-... 

Final remarks. The 14C-KIE and 2H-SKIE data presented in this Section (VLB) clearly indicate the usefulness of isotope effect methodology in studies of mechanistic details of thermally induced Claisen rearrangement, which provides a synthetic route to y,5-unsaturatcd carbonyl compounds. The primary and secondary 14C KIE supplement strongly the deuterium SKIE. Especially easy for interpretation are 14C and 2H isotope... 

Abdrakhmanov and co-workers observed the cycloaddition of N-( 1 -methyl-2-butenyl)aniline or 2-(l-methyl-2-butenyl)aniline with PdCyDMSO to give a 69% yield of a mixture of 2-ethyl-3-methylindole and 2,4-dimethylquinoline [87]. The authors propose that a Claisen rearrangement is initially involved. A similar oxidative cyclization of a 5-amino-indoleacrylate was the starting point for syntheses of CC-1065 and related compounds [88],... 

The Claisen rearrangement of propargyl vinyl ethers directly delivers the allene no equilibrium is observed. This reaction was also successful with complex substrates in order to show this, of numerous examples [375, 513-536], the compounds 159 [537] and 161 [538] are depicted (Scheme 1.71). 

Alkoxyallenes turned out to be excellent starting materials also for the synthesis of highly functionalized 1,3-dienes, two examples being depicted in Schemes 8.61 and 8.62. As described by Kantlehner et al., 1,3-dienes such as 238 were obtained from methoxyallene derivative 50 by condensation with CH-acidic compounds 237 [135]. Hoppe and co-workers explored the stereochemical course of the allene Claisen rearrangement under Johnson s conditions, e.g. the reaction of 239 with trimethyl orthoacetate, which furnished intermediate 240 followed by rearrangement to the isomeric dienes 241a,b [136],... 

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