Enantioselective Intermolecular Aldehyde–Ketone Cross‐Coupling through an Enzymatic Carboligation Reaction

Lehwald, Patrizia; Richter, Michael; Röhr, Caroline; Liu, Hung‐wen; Müller, Michael

doi:10.1002/anie.200906181

Cited by 84 publications

(60 citation statements)

References 23 publications

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“…As an example,b enzaldehyde lyase (BAL) from Pseudomonas fluorescens catalyzes the reaction of benzaldehyde with 2methyl propionaldehyde as an acceptor.Akinetic resolution process is observed to afford a-hydroxy ketone adducts with good diastereo-and excellent enantiocontrol (Figure 24). [93] Beyond 1,2-addition to aldehydes and ketones,i ns itu generated acyl anion equivalents can also engage in 1,4addition with unsaturated substrates,atransformation commonly referred to as the "Stetter reaction" (Figure 26). Va rious types of ketones 109 can be used as electrophilic acceptors,i ncluding simple ketones,d iketones, and b-ketoesters.…”

Section: Umpolung Strategiesmentioning

confidence: 99%

Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

et al. 2017

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Recent developments of stereoselective biocatalytic and chemocatalytic methods are discussed. The review provides a guide to the use of biocatalytic methods in the area of chemical synthesis with focused attention on retrosynthetic considerations and analysis. The transformations presented are organized according to bond disconnections and attendant synthetic methods. The review is expected to lead to better understanding of the characteristics and distinctions of the two complementary approaches. It depicts for researchers in bio- and chemocatalysis a road map of challenges and opportunities for the evolution (and at times revolution) in chemical synthesis.

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Section: Umpolung Strategiesmentioning

confidence: 99%

Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

et al. 2017

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“…Branched-chain sugars [3,11,102] are frequently employed in bacterial cell wall formation, where they serve structural roles or contribute to antigenic determinants [61]. In deoxy sugar combinatorial biosynthesis, enzymes capable of branching could allow access to more complex carbohydrates [103]. The caprazamycins ( 80 ), liposidomycins ( 81 ), murraymycins, and related compounds are nucleoside antibiotics that feature a unique diazopanone moiety [104,105].…”

Section: Glycine Additionmentioning

confidence: 99%

Mechanisms and structures of vitamin B6-dependent enzymes involved in deoxy sugar biosynthesis

Romo

Liu²

2011

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

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PLP is well-regarded for its role as a coenzyme in a number of diverse enzymatic reactions. Transamination, deoxygenation, and aldol reactions mediated by PLP-dependent enzymes enliven and enrich deoxy sugar biosynthesis, endowing these compounds with unique structures and contributing to their roles as determinants of biological activity in many natural products. The importance of deoxy amino sugars in natural product biosynthesis has spurred several recent structural investigations of sugar aminotransferases. The structure of a PMP-dependent enzyme catalyzing the C-3 deoxygenation reaction in the biosynthesis of ascarylose was also determined. These studies, and the crystal structures they have provided, offer a wealth of new insights regarding the enzymology of PLP/PMP-dependent enzymes in deoxy sugar biosynthesis. In this review, we consider these recent achievements in the structural biology of deoxy sugar biosynthetic enzymes and the important implications they hold for understanding enzyme catalysis and natural product biosynthesis in general.

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“…Indeed, aroma compounds such as linalool and ␣-terpineol displaying a chiral tertiary alcohol functionality, that is a structural motif widespread among many natural products including flavor compounds, are typically prepared using hydrolases for the kinetic resolution of racemates [15][16][17][18][19]. On the other hand, it has also been demonstrated in methodological studies that carboligation reactions catalyzed by thiamine diphosphate (ThDP)-dependent enzymes can be successfully employed for the direct, enantioselective synthesis of optically pure tertiary alcohols through umpolung strategies [20,21]. Quite recently, the chiral tertiary alcohol 3-hydroxy-3-methylnonane-2,4-dione 3 (Scheme 1) has been recognized as one of the main components of the volatile fraction responsible for the characteristic flavor of green tea brews.…”

Section: Introductionmentioning

confidence: 99%