Rearrangement acylals

H-Azepin-2-one, 3-acetyl-synthesis, 7, 542-543 3/f-Azepin-2-one, 7-acetyl-synthesis, 7, 542-543 3H-Azepin-2-one, 3-acyl-rearrangements, 7, 505 3/f-Azepin-2-one, 3-acyl-2-alkoxy-formation, 7, 542-543 3H-Azepin-2-one, 1-alkyl-rearrangements, 7, 505 3/f-Azepin-2-one, N-alkyl-synthesis, 7, 511 Azepinones... 

Azirine, C-acyl-rearrangement oxazoles from, 6, 223 Azirine, allyl-... 

Methyl 2,4,6-tri-0-acetyl-/3-D-glucopyranoside afforded the 2-methyl ether in 66% yield on methylation under the Purdie conditions.566 A similar 0-2 — 0-3 acyl rearrangement was observed on... 

The kinetics, activation parameters, and substituent effects attending the acyl rearrangements of acyloxycarbenes have been analyzed in detail from both the experimental and theoretical viewpoints further discussion will appear below in Section VHD. 

Fries rearrangement.1 Rearrangement of phenyl esters with Lewis acids results in a mixture of ortho- and para-phenolic ketones. In contrast, reaction of an o-bromophenyl ester with sec-butyllithium results in exclusive formation of the orf/jo-phenolic ketone by an intramolecular acyl rearrangement.2... 

Pathways involving alkyl-acyl rearrangements are proposed to explain the carbonylation of a-bonded alkoxy complexes (17). The stereochemistry of the products indicates that the ester group replaces Pd with retention of configuration at the carbon to which Pd is o-bonded. In all these studies with unconjugated dienes the nature of carbonylation products to be expected is clearly influenced by the geometry of the intermediate Pd complexes. 

Iy2-Acyl rearrangement of a, -epoxy ketones. This rearrangement can be used for synthesis of cyclic spiro-1,3-ketones. Thus the 2-cycloheptylidenecyclopenta-none oxide 1 rearranges in the presence of BF3 etherate at 25° within one minute to the spiro-1,3-diketone 2 in 91% yield.1... 

H-Azepin-2-one, 3-acetyl-synthesis, 7, 542-543 3H-Azepin-2-one, 7-acetyl-synthesis, 7, 542-543 3H-Azepin-2-one, 3-acyl-rearrangements, 7, 505... 

The [1/3] acyl rearrangement of cyclobutanones and the formation of ketoaldehydes both represent formal intramolecular trapping of biradical intermediates. 

Fig. 2. Scheme of protein splieing. Cleavage pathway proposed for intein that possesses a cysteine residue in eaeh spliee junetion. In the initial step a linear thioester intermediate is formed by an N-S acyl rearrangement at Cysi (N-terminal amino acid of the intein). Next, traw -thioesterification that involves nucleophilic attack of the side-... 

Fig. 2. Continued) chain of Cys+i (N-terminal amino acid of the C-extein) on the thioester results in the formation of a branched intermediate. Excision of the intein occurs by peptide bond cleavage coupled to succinimide formation at the C-terminal asparagine of the intein. The ligated exteins undergo a spontaneous S-N acyl rearrangement to create a stable amide bond.

Figure 4 Mechanism of trans-protein splicing, (a) Initial association of the intein halves to form a functional intein. (b) Activation of the N-terminal splice-junction via an N-S acyl shift, (c) Formation of a branched intermediate upon transthioesterification. (d) Branch resolution and intein release by succinimide formation. Spontaneous S-N acyl rearrangement yields the processed product with a native peptide backbone.

Anthracene, 9,10-dihydro-9,9-dimethyl-as antidepressant, 1, 169 Anthracene, 1,4,5,8,9-pentamethyl-synthesis, 2, 537 Anthracyclinones synthesis, 1, 414, 4, 700 Anthramycin synthesis, 7, 614 Anthranil, 3-acyl-rearrangement, 5, 93 Anthranil, 3-aiyl-acridones from, 2, 93 thermolysis, 5, 91 Anthranil, 3-(imidazol-2-yl)-rearrangement, 5, 433 Anthranil, 6-nitro-reactions... 

---