Cofactor-independent C–C bond cleavage reactions catalyzed by the AlpJ family of oxygenases in atypical angucycline biosynthesis

• Jinmin Gao,
• Liyuan Li,
• Shijie Shen,
• Guomin Ai,
• Bin Wang,
• Fang Guo,
• Tongjian Yang,
• Hui Han,
• Zhengren Xu,
• Guohui Pan and
• Keqiang Fan

Beilstein J. Org. Chem. 2024, 20, 1198–1206, doi:10.3762/bjoc.20.102

• 2 via Baeyer–Villiger oxidation, followed by hydrolysis to yield another crucial aldehyde/acid intermediate 3 [11][15]. Commencing from 3, diverse ring rearrangement reactions can occur, leading to the formation of distinct products. In the AlpJ-catalyzed reaction, compound 3 undergoes ring

(Bio)isosteres of ortho- and meta-substituted benzenes

• H. Erik Diepers and
• Johannes C. L. Walker

Beilstein J. Org. Chem. 2024, 20, 859–890, doi:10.3762/bjoc.20.78

• -workers also reported the modification of these 1,2-BCHs to increase the number of derivatives accessible using this approach (Scheme 3B) [38]. Transformation of the naphthyl ketone moiety of BCH (±)-25d by Baeyer–Villiger oxidation followed by hydrolysis gave carboxylic acid (±)-26. Through Curtius

• nitrile group (to (±)-35 and (±)-37), Baeyer–Villiger oxidation (to (±)-38 and (±)-39), reduction of the nitrile group (to (±)-36) and Beckman rearrangement (to (±)-40). A mechanistically related synthesis of 1,2-BCHs was published recently by Wang and co-workers (not shown) [39]. They employed a

Photochromic derivatives of indigo: historical overview of development, challenges and applications

• Gökhan Kaplan,
• Zeynel Seferoğlu and
• Daria V. Berdnikova

Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23

• using heme-containing oxygenases (cytochrome P450 monooxygenases, styrene/indole monooxygenases, flavin-containing monooxygenases, Baeyer–Villiger monooxygenases, etc.) or non-heme iron oxygenases (naphthalene dioxygenases, multicomponent phenol hydroxylases) [5][6][7][8]. The synthetic approaches

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

• enantiomeric purity. Further transformations of the products were demonstrated in several examples, including reduction, acidic deprotection and subsequent base-mediated cyclization, or Baeyer–Villiger oxidation. At about the same time, Huang and co-workers have developed similar asymmetric tandem sequences

Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities

• Jorge de Lima Neto and
• Paulo Henrique Menezes

Beilstein J. Org. Chem. 2023, 19, 399–427, doi:10.3762/bjoc.19.31

• their anti-inflammatory activity (see Section 3). Reaction of compounds 166 and 167 gave the corresponding diaryl ether 168, which was converted to phenol 169 using a Baeyer–Villiger oxidation reaction followed by hydrolysis. Subsequent phenol allylation reaction followed by Claisen rearrangement led to

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• in oxidative processes for the activation of electrophilic properties of unsaturated substrates or for the activation of hydroperoxide oxidative properties. In Scheme 4A the proposed transition state for the Brønsted acid-catalyzed asymmetric Baeyer–Villiger reaction is shown, in which the

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

• [158]. The synthesis started with a cyclopentene derivative, obtained after two steps from a diol via tosylation/displacement strategy with Me2CuLi·LiI. Then, after a Lewis acid-promoted cycloaddition, the alkylation of the α-carbon atom followed by regioselective Baeyer–Villiger oxidation provided the

Synthesis of legonmycins A and B, C(7a)-hydroxylated bacterial pyrrolizidines

• Wilfred J. M. Lewis,
• David M. Shaw and
• Jeremy Robertson

Beilstein J. Org. Chem. 2021, 17, 334–342, doi:10.3762/bjoc.17.31

• Baeyer–Villiger-type ring expansion, hydrolysis and decarboxylation, cyclization and dehydration, and finally hydroxylation at C(7a). Just one month later, Bode reported the identification of an unknown gene cluster in the symbiotic bacterium Xenorhabdus stockiae [23]. Cloning and expression of this

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• reported hydroxysumanene 68 by means of a Baeyer–Villiger oxidation reaction of acyl- or formylsumanene derivatives in the presence of m-chloroperbenzoic acid (m-CPBA) followed by acid-catalyzed solvolysis in 10% HCl/MeOH (Scheme 15) [46]. Interestingly, it was found from both theoretically as well as

Copper-catalysed alkylation of heterocyclic acceptors with organometallic reagents

• Yafei Guo and
• Syuzanna R. Harutyunyan

Beilstein J. Org. Chem. 2020, 16, 1006–1021, doi:10.3762/bjoc.16.90

• access various derivatives, such as 12 and 13, derived from the trapping and Baeyer–Villiger oxidation of 11, respectively, or compound 16, obtained via the ring opening reaction of 15 with an amine (Scheme 5). Taking the enolate intermediate derived from the addition of EtMgBr to coumarin as an example

Bipolenins K–N: New sesquiterpenoids from the fungal plant pathogen Bipolaris sorokiniana

• Chin-Soon Phan,
• Hang Li,
• Simon Kessler,
• Peter S. Solomon,
• Andrew M. Piggott and
• Yit-Heng Chooi

Beilstein J. Org. Chem. 2019, 15, 2020–2028, doi:10.3762/bjoc.15.198

• at the nerolidyl cation (Figure 5b) [28][29][30][31]. The biosynthesis of 1–8 and 10–11 are likely to be derived from sativene with a key oxidation at C-15 followed by a Baeyer–Villiger oxidation to break the C-14–C-15 bond (Figure 5c). Based on an isotope labelling study, the γ-butyrolactone moiety

• on 11 has been proposed to be derived from oxaloacetic acid or similar TCA-cycle intermediates [32]. Compound 9, which contains the seco-longifolene scaffold, is likely to be derived from longifolene via a similar Baeyer–Villiger mechanism proposed above for 1–8 and 10 and 11. Several sativene-type

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

• , inexpensive, water-tolerant Lewis acid catalyst in the formation of both carbon–carbon and carbon–heteroatom bonds, and thereby the formation of various biologically promising organic compounds [68]. Important advances in scandium-catalyzed chemistry include [4 + 2] and [2 + 2] cycloaddition reactions, Baeyer

• –Villiger reactions, epoxidations of alkenes, intramolecular ring expansions, hydroaminations, and amination reactions and carbonyl–ene reactions for the formation of C–C bond. Scandium-catalyzed reactions represented remarkable enantioselectivities [79][80][81]. Recently the group of Rani has developed fly

Volatiles from the xylarialean fungus Hypoxylon invadens

• Jeroen S. Dickschat,
• Tao Wang and
• Marc Stadler

Beilstein J. Org. Chem. 2018, 14, 734–746, doi:10.3762/bjoc.14.62

• derivative to the corresponding aldehyde 12 that upon O-methylation (green), likely with S-adenosylmethionine, would result in 17. The alternative oxidation of 12 by a Baeyer–Villiger monooxygenase could result in the insertion of an oxygen (blue) to yield the formate ester 21, followed by ester hydrolysis

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

• moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related

• processes of important natural and synthetic peroxides are discussed separately. Keywords: artemisinin; Baeyer−Villiger; Criegee; Hock; peroxide; rearrangement; Introduction The chemistry of organic peroxides has more than a hundred-year history. Currently, organic peroxides are widely used as oxidizing

• Baeyer−Villiger oxidation and it is one of the methods for the synthesis of commercially important caprolactone from cyclohexanone with peracetic acid [55][56]. Autoxidation processes with formation of hydroperoxides and their subsequent free-radical transformations with generation of carbon- and oxygen

Biosynthesis of oxygen and nitrogen-containing heterocycles in polyketides

• Franziska Hemmerling and
• Frank Hahn

Beilstein J. Org. Chem. 2016, 12, 1512–1550, doi:10.3762/bjoc.12.148

• participation of the FMO MoxY in a Baeyer–Villiger oxidation, which yields versiconal acetate (104) [93][94]. This is then hydrolysed by a cytosolic esterase (putatively also coded in the aflatoxin gene cluster as estA) to versiconal (105) [95]. The bisfuran moiety of versicolorin B (106), which is crucial for

• disruption experiments by Cary et al. have shown that the NADH-dependent oxidoreductase AflX also takes part in the conversion [102]. Furthermore, the putative Baeyer–Villiger oxidase AflY was shown to be essential for demethylsterigmatocystin (107) formation and has been rationalised to form an intermediate

Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes

• Norbert Vida,
• Jiří Václavík and
• Petr Beier

Beilstein J. Org. Chem. 2016, 12, 110–116, doi:10.3762/bjoc.12.12

• transformations: electrophilic aromatic hydroxylation to the intermediate 6, oxidation to ortho-benzoquinone 7, Baeyer–Villiger (BV) oxidation, hydrolysis to muconic acid derivative 8, and finally intramolecular conjugate addition affording 3. Under certain conditions, small amounts of intermediates 6 and 8 were

Aspergiloid I, an unprecedented spirolactone norditerpenoid from the plant-derived endophytic fungus Aspergillus sp. YXf3

• Zhi Kai Guo,
• Rong Wang,
• Wei Huang,
• Xiao Nian Li,
• Rong Jiang,
• Ren Xiang Tan and
• Hui Ming Ge

Beilstein J. Org. Chem. 2014, 10, 2677–2682, doi:10.3762/bjoc.10.282

• intermediate 2 undergoes decarboxylation to form 3 through Baeyer–Villiger oxidation to form the 7-membered lactone 4, then hydrolyzation, decarboxylation and lactonization to finally give aspergiloid I (1). Aspergiloid I (1) was evaluated for its cytotoxicity against eleven human cancer cell lines, K562

Structure elucidation of female-specific volatiles released by the parasitoid wasp Trichogramma turkestanica (Hymenoptera: Trichogrammatidae)

• Armin Tröger,
• Teris A. van Beek,
• Martinus E. Huigens,
• Isabel M. M. S. Silva,
• Maarten A. Posthumus and
• Wittko Francke

Beilstein J. Org. Chem. 2014, 10, 767–773, doi:10.3762/bjoc.10.72

• -cis-2,4,6-trimethylcyclohexanone. Subsequent Baeyer–Villiger oxidation, followed by reduction of the obtained lactone, yielded syn,syn-2,4-dimethylheptan-1,6-diol 16 (Figure 4). Protection of the primary hydroxy group gave 17 followed by a Mitsunobu sequence involving the secondary hydroxy group

Self-assembly of metallosupramolecular rhombi from chiral concave 9,9’-spirobifluorene-derived bis(pyridine) ligands

• Rainer Hovorka,
• Sophie Hytteballe,
• Torsten Piehler,
• Georg Meyer-Eppler,
• Filip Topić,
• Kari Rissanen,
• Marianne Engeser and
• Arne Lützen

Beilstein J. Org. Chem. 2014, 10, 432–441, doi:10.3762/bjoc.10.40

• subjected to an acid-mediated condensation to give the 9,9’-spirobifluorene. Friedel–Crafts acylation with acetyl chloride gave rise to the racemic 2,2’-diketone which was transformed to the racemic diester in a Baeyer–Villiger oxidation. Saponification of the ester functions then afforded (rac)-1. One part

Branching out at C-2 of septanosides. Synthesis of 2-deoxy-2-C-alkyl/aryl septanosides from a bromo-oxepine

• Supriya Dey and
• Narayanaswamy Jayaraman

Beilstein J. Org. Chem. 2012, 8, 522–527, doi:10.3762/bjoc.8.59

• metathesis reactions of appropriately installed diene derivatives [11][12][13]; (iv) ring expansion of 1,2-cyclopropanated sugars [14][15][16][17]; (v) Baeyer–Villiger oxidation of inositol derivatives [18][19] and (vi) electrophile-induced cyclization [20]. We recently developed a new methodology to prepare

Reciprocal polyhedra and the Euler relationship: cage hydrocarbons, C_nH_n and closo-boranes [B_xH_x]²⁻

• Michael J. McGlinchey and
• Henning Hopf

Beilstein J. Org. Chem. 2011, 7, 222–233, doi:10.3762/bjoc.7.30

• produce the parent system 12. More realistically, one can see the obvious similarity to the conversion of homopenta-prismanone, 41, to pentaprismane, 11, which was successfully accomplished via Baeyer–Villiger oxidation, acyloin coupling and decarboxylation. Thus, one might anticipate that such an

The development and evaluation of a continuous flow process for the lipase- mediated oxidation of alkenes

• Charlotte Wiles,
• Marcus J. Hammond and
• Paul Watts

Beilstein J. Org. Chem. 2009, 5, No. 27, doi:10.3762/bjoc.5.27

• biocatalyst with respect to peracid formation, facilitating a series of oxidations including alkenes [21] and ketones via the Baeyer–Villiger reaction [22] and retaining the broad substrate specificity of Candida antarctica lipase B. In the past decade micro reactors, and more generically continuous flow

Recent progress on the total synthesis of acetogenins from Annonaceae

• Nianguang Li,
• Zhihao Shi,
• Yuping Tang,
• Jianwei Chen and
• Xiang Li

Beilstein J. Org. Chem. 2008, 4, No. 48, doi:10.3762/bjoc.4.48

Towards practical biocatalytic Baeyer- Villiger reactions: applying a thermostable enzyme in the gram- scale synthesis of optically- active lactones in a two-liquid- phase system

• Frank Schulz,
• François Leca,
• Frank Hollmann and
• Manfred T. Reetz

Beilstein J. Org. Chem. 2005, 1, No. 10, doi:10.1186/1860-5397-1-10

• Frank Schulz Francois Leca Frank Hollmann Manfred T. Reetz Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim/Ruhr, Germany 10.1186/1860-5397-1-10 Abstract Baeyer-Villiger monooxygenases (BVMOs) are extremely promising catalysts useful for enantioselective oxidation

• shows that the thermally stable phenylacetone monooxygenase (PAMO) and recently engineered mutants can be used as a practical catalysts for enantioselective Baeyer-Villiger oxidations of several ketones on a preparative scale under in vitro conditions. For this purpose several parameters such as buffer

• well versed in the use of enzymes. Keywords: Baeyer-Villiger oxidation; monooxygenases; two-liquid-phase system; stereoselective catalysis; biocatalysis; Introduction First reported in 1899, the Baeyer-Villiger (BV) reaction of ketones with formation of esters or lactones has become a fundamental and