Baeyer-Villiger transformation

The highest priority ring disconnective T-goals for 272 are those which disconnect a cocyclic 5,5-fusion bond and offexendo bond pair. The internal ketene-olefin cycloaddition in tactical combination with the Baeyer-Villiger transform is well suited to the double disconnection of such a cyclopentane-y-lactone ring pair. 

The Baeyer-Villiger transformation of several protected derivatives having a free ketone group has been effected by m-chloroperoxybenzoic acid. Thus, 1,6-anhydro-3,4-0-isopropylidene-/f-D-/yxn-hexopyranos-2-ulose (28) was converted into the cyclic, orthoacid anhydride 29.67 As an additional example, the Baeyer-Villiger oxidation of Ferrier carbocyclization products derived from D-glucose afforded 5-deoxyhexofuranosiduronic acids, via the ring-expanded lactonic intermediates68 (Scheme 12). 

Scheme 9.132. A representation of the Mn -catalyzed oxygen (O2) oxidation of ethanal (acetaldehyde, CHaCHO) to perethanoic acid (peracetic acid.CHaCOaH) and the snbseqnent transformation of the peracid and additional ethanal (acetaldehyde, CH3CHO) to ethanoic acid (acetic acid, CHaC02H), via a Baeyer-Villiger transformation, or to ethanoic anhydride [acetic anhydride, (CHaCO)20].

Figure 5 Baeyer-Villiger transformation of (H-)-camphor by 2,5-DKCMO from Pseudomonas putida. (From Ref. 6.)...

Erythronolide B, the biosynthetic progenitor of the erythromycin antibiotics, was synthesized for the first time, using as a key step a new method for macrolactone ring closure (double activation) which had been devised specifically for this problem. Retrosynthetic simplification included the clearance of the stereocenters at carbons 10 and 11 and the disconnection of the 9,10-bond, leading to precursors A and B. Cyclic stereocontrol and especially the Baeyer-Villiger and halolactonization transforms played a major role in the retrosynthetic simplification of B which was synthesized starting from 2,4,6-trimethylphenol. 

Transformation of cyclic ketones into lactones by Baeyer-Villiger oxidation 99EJ0737. 

The pseudobenzylisoquinoline alkaloids are fairly widespread in nature, being found among members of Berberidaceae, Annonaceae, Fumariaceae, and Ranunculaceae. The biogenesis of the pseudobenzylisoquinoline alkaloids assumes their formation from protoberberinium salts by C-8—C-8a bond scission in a Baeyer-Villiger-type oxidative rearrangement to produce the enamides of type 73 and 74. These amides may be further biotransformed either to rugosinone (76) type alkaloids by hydrolytic N-deformylation followed by oxidation or to ledecorine (75) by enzymatic reduction. These transformations were corroborated by in vitro studies (80-82). It is suggested that enamide seco alkaloids may be precursors of aporphine alkaloids (80), on one hand, and of cularine alkaloids (77), on the other. 

Alphand, V., Archelas, A. andFurstoss, R., Microbial transformations 16. One-step synthesis of a pivotal prostaglandin chiral synthon via a highly enantioselective microbiological Baeyer-Villiger-type reaction. Tetrahedron Lett., 1989, 30, 3663. 

Baeyer-Villiger oxidation of ketone 104 with metachloroperbenzoic (MCPBA) acid afforded lactone 105 (86 %). There was no detectable trace of the product resulting from oxygen insertion between centers C(2) and C(3). On treatment with acidic methanol, 105 was transformed into a 90 4 mixture of a- and p-acetal-acids 106 (94 %). Treatment with 2 equivalents of MeLi afforded methyl ketone 107... 

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