A short stereoselective synthesis of (+)- and (−)-2-oxabicyclo[3.3.0]oct-6-en-3-one by intramolecular carbon–hydrogen insertion catalyzed by chiral dirhodium(II) carboxamidates

Doyle, Michael P.; Catino, Arthur J.

doi:10.1016/s0957-4166(03)00083-1

Cited by 31 publications

(11 citation statements)

References 23 publications

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“…Data were in agreement with the literature. 30 Waxy colourless solid. 1 H NMR (400 MHz, CDCl 3 ) δ 5.80 (dq, J = 4.5, 2.0 Hz, 1H), 5.58 (dq, J = 6.0, 2.0 Hz, 1H), 5.16-5.11 (m, 1H), 3.51 (ddq, J = 9.5, 6.0, 2.0 Hz, 1H), 2.77 (dd, J = 18.0, 9.5 Hz, 1H), 2.72 (sext, J = 2.0 Hz, 2H), 2.45 (dd, J = 18.0, 2.0 Hz, 1H); 13…”

Section: Chiral Capillary Gcmentioning

confidence: 99%

E. coli cells expressing the Baeyer–Villiger monooxygenase ‘MO14’ (ro03437) from Rhodococcus jostii RHA1 catalyse the gram-scale resolution of a bicyclic ketone in a fermentor

et al. 2015

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The Baeyer-Villiger monooxygenase (BVMO) 'MO14' from Rhodococcus jostii RHA1, is an enantioselective BVMO that catalyses the resolution of the model ketone substrate bicyclo[3.2.0]hept-2-en-6-one to the (1S,5R)-2-oxa lactone and the residual (1S,5R)-substrate enantiomer. This regio-plus enantioselective behaviour is highly unusual for BVMOs, which often perform enantiodivergent biotransformations of this substrate. The scaleability of the transformation was investigated using fermentor-based experiments, in which variables including gene codon optimisation, temperature and substrate concentration were investigated. E. coli cells expressing MO14 catalysed the resolution of bicyclo[3.2.0]hept-2-en-6-one to yield (1S,5R)-2-oxa lactone of >99% ee and (1S,5R)-ketone of 96% ee after 14 h at a temperature of 16 °C and a substrate concentration of 0.5 g L(-1) (4.5 mM). MO14 is thus a promising biocatalyst for the production of enantio-enriched ketones and lactones derived from the [3.2.0] platform.

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Section: Chiral Capillary Gcmentioning

confidence: 99%

E. coli cells expressing the Baeyer–Villiger monooxygenase ‘MO14’ (ro03437) from Rhodococcus jostii RHA1 catalyse the gram-scale resolution of a bicyclic ketone in a fermentor

et al. 2015

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“…Utilizing substrates containing methyl groups at the site of the insertion event and a single electron withdrawing group on the diazo compound, 64 was produced in up to 44% ee [76]. Doyle, on the other hand, obtained superior results with simpler 3-substituted cyclopentene system 65 (Scheme 14, right) [77]. When heteroatom-rich Rh 2 (4S-MPPIM) 4 (28a) was used as the catalyst, 66 was obtained in 91% ee.…”

Section: Desymmetrization Reactionsmentioning

confidence: 99%

Functionalization of Carbon–Hydrogen Bonds Through Transition Metal Carbenoid Insertion

Davies

Dick

2009

C-H Activation

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The functionalization of carbon-hydrogen bonds through transition metal carbenoid insertion is becoming a powerful method for the construction of new carbon-carbon bonds in organic synthesis. This chapter will highlight recent developments in this field, while placing it within its historical context. Intramolecular carbenoid C-H insertion will be covered first, focusing on formation of three-and six-membered rings, as well as the use of nontraditional substrates. Additionally, the most recent progress in asymmetric catalysis will be discussed. The bulk of the chapter will concentrate on intermolecular transformations, emphasizing both the effect of substrate structure and the influence of carbene substituent electronics on the regioselectivity of the reactions. Vinyldiazoacetates will be covered as a distinct class of carbenoid precursors, as they have been shown to initiate a variety of unique transformations, such as the combined C-H activation/Cope rearrangement. Finally, the synthetic utility of carbenoid C-H insertion reactions, both intra-and intermolecular, will be displayed through their use in the total syntheses of a number of natural products and pharmaceuticals.

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“…Configurational match/mismatch governs these reactions so that different products may be produced in high yield and selectivity when enantiomeric catalysts are applied to the same substrate [61,62], as illustrated by the reaction processes in Scheme 15.8 [61]. Additional examples in the steroidal field have also been reported [66].…”

Section: Catalytic Asymmetric Carbon-hydrogen Insertionmentioning

confidence: 99%

Chiral Dirhodium(II) Carboxamidates for Asymmetric Cyclopropanation and Carbon–Hydrogen Insertion Reactions

Doyle

2005

Modern Rhodium‐Catalyzed Organic Reactions

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In 1989-1990 three groups published initial results relating to the development of dirhodium(II) catalysts for asymmetric transformations of diazo compounds [1][2][3]. Two focused on amino acid carboxylate ligands [1,2], and one of them fortuitously found that prolinate ligands had unusual selectivity in reactions of diazoacetates and related substrates [2], even though the ligand's chiral centers lie far from the axial sites of dirhodium(II), which is where the carbene intermediate is formed. This discovery has led to very significant undertakings by Davies, particularly with aryl-and vinyldiazoacetates [4-8], but they have already been described in Chapter 14.On the basis of reports by Bear and co-workers [10-12] and the discovery that carboxamidate ligands could be introduced onto dirhodium(II) by semi-automated methods [13], Doyle and co-workers began their development of carboxamidate ligands for dirhodium with oxazolidinones (for example, 1 and 2), but with limited success in achieving high enantiocontrol [3]. Only when a carboxylate attachment, as in pyrrolidinone 3, rather than an isopropyl or benzyl group, as in 1 or 2, was placed in proximity to the reaction center, could high enantiocontrol be achieved [14]. The key developments here were: 1) the methodology for the semi-automated synthesis of dirhodium(II) carboxamidates by trapping acetic acid with sodium carbonate in a Soxhlet extraction apparatus (Eq. 1) [15]; and 2) the discovery of the high selectivity enhancement afforded by the carboxylate attachment [16]. Scheme 15.6 (cont.) Scheme 15.7 Synthesis of 2-deoxyxylolactone. 93 : 7

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A short stereoselective synthesis of (+)- and (−)-2-oxabicyclo[3.3.0]oct-6-en-3-one by intramolecular carbon–hydrogen insertion catalyzed by chiral dirhodium(II) carboxamidates

Cited by 31 publications

References 23 publications

E. coli cells expressing the Baeyer–Villiger monooxygenase ‘MO14’ (ro03437) from Rhodococcus jostii RHA1 catalyse the gram-scale resolution of a bicyclic ketone in a fermentor

E. coli cells expressing the Baeyer–Villiger monooxygenase ‘MO14’ (ro03437) from Rhodococcus jostii RHA1 catalyse the gram-scale resolution of a bicyclic ketone in a fermentor

Functionalization of Carbon–Hydrogen Bonds Through Transition Metal Carbenoid Insertion

Chiral Dirhodium(II) Carboxamidates for Asymmetric Cyclopropanation and Carbon–Hydrogen Insertion Reactions

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