A practical synthesis of enantiopure β-methyltryptophan ethyl ester for a preparation of diabetes drug

Sawai, Yasuhiro; Mizuno, Masahiro; Itô, Tatsuya; Kawakami, Junichi; Yamano, Mitsuhisa

doi:10.1016/j.tet.2009.06.027

Cited by 15 publications

(12 citation statements)

References 37 publications

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“…Researchers at Takeda reported CIDT of racemic αnitro ester 30, starting with a diastereomeric syn-30/ anti-30 mixture in a 6:4 ratio (Scheme 13). [63] Scheme 9. CIDT in synthesis of (2S,3R,4S)-4-hydroxyisoleucine (18).…”

Section: Base-mediated Deprotonationmentioning

confidence: 99%

State of the Art in Crystallization‐Induced Diastereomer Transformations

Kolarovič

Jakubec

2021

Adv Synth Catal

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Crystallization-induced diastereomer transformations (CIDT) enable isolation of the target compounds in high enantio-and diastereomeric purities and with up to quantitative yields simply by filtration. Numerous inspiring examples of this appealing synthetic strategy reported over the last fifteen years are reviewed. Important observations along with aspects to consider when designing CIDT experiments are discussed. 3.3. Formation of Schiff Base or Related Intermediates 3.4. Aza-Michael and Mannich-Type Reactions 3.5. Strecker Reaction 3.6. Aldol Reactions 3.7. Epimerization at Phosphorus-Based Stereocenters 3.8. Racemization/Epimerization through Change of Conformation 3.9. Miscellaneous Examples of CIDT 4.Conclusions and Perspectives

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Section: Base-mediated Deprotonationmentioning

confidence: 99%

State of the Art in Crystallization‐Induced Diastereomer Transformations

Kolarovič

Jakubec

2021

Adv Synth Catal

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“…Beta‐branched amino acids are found in many useful bioactive natural products and pharmaceuticals; however, the presence of two adjacent chiral centers makes them particularly challenging to synthesize [60,61] . Buller's team engineered their stand‐alone TrpB to accept l ‐threonine as the electrophile to produce β‐methylTrp (Scheme 3b) [62] .…”

Section: Synthesis Of Noncanonical Trp Derivativesmentioning

confidence: 99%

“…Beta-branched amino acids are found in many useful bioactive natural products and pharmaceuticals; however, the presence of two adjacent chiral centers makes them particularly challenging to synthesize. [60,61] Buller's team engineered their standalone TrpB to accept l-threonine as the electrophile to produce β-methylTrp (Scheme 3b). [62] Unlike in earlier works, where modified electrophiles ultimately produced the same aminoacrylate as Ser, [63,64] the use of Thr generated an entirely new βsubstituted amino-acrylate-like species (amino-crotonate) that diastereoselectively formed a second chiral center upon CÀ C bond formation.…”

Section: β-Branched Trpsmentioning

confidence: 99%

Tryptophan Synthase: Biocatalyst Extraordinaire

2020

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Tryptophan synthase (TrpS) has emerged as a paragon of noncanonical amino acid (ncAA) synthesis and is an ideal biocatalyst for synthetic and biological applications. TrpS catalyzes an irreversible, CC bond forming reaction between indole and serine (Ser) to make L-tryptophan (Trp); native TrpS complexes possess fairly broad specificity for indole analogs, but are difficult to engineer to extend substrate scope or to confer other useful properties due to allosteric constraints and their heterodimeric structure. Directed evolution freed the catalytically relevant TrpS β-subunit (TrpB) from allosteric regulation by its TrpA partner and has enabled dramatic expansion of the enzyme's substrate scope. This review examines the long and storied career of TrpS from the perspective of its application in ncAA synthesis and biocatalytic cascades.

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“…[14][15][16][17][18] For example, traditional organic synthesis of (2S, 3S)-β-methyltryptophan (β-MeTrp) requires multiple steps that incorporate protecting groups, hazardous reagents, and expensive metal catalysts. [19,20] To take full advantage of these bioactive molecules, an improved methodology is needed to synthesize β-branched ncAAs. Enzymes offer an efficient and sustainable alternative to chemical synthesis and are routinely used to generate enantiopure amino acids from simple materials without the need for protecting groups.…”

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confidence: 99%

Engineered Biosynthesis of β‐Alkyl Tryptophan Analogues

et al. 2018

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Non-canonical amino acids (ncAAs) with dual stereocenters at the α and β positions are valuable precursors to natural products and therapeutics. Despite the potential applications of such bioactive β-branched ncAAs, their availability is limited due to the inefficiency of the multi-step methods used to prepare them. Here we report a stereoselective biocatalytic synthesis of β-branched tryptophan analogs using an engineered variant of Pyrococcus furiosus tryptophan synthase (PfTrpB), PfTrpB

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A practical synthesis of enantiopure β-methyltryptophan ethyl ester for a preparation of diabetes drug

Cited by 15 publications

References 37 publications

State of the Art in Crystallization‐Induced Diastereomer Transformations

State of the Art in Crystallization‐Induced Diastereomer Transformations

Tryptophan Synthase: Biocatalyst Extraordinaire

Engineered Biosynthesis of β‐Alkyl Tryptophan Analogues

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