The Synthesis and Metabolism of 2,3-Dihydro-L-tryptophan and 2,3-Dihydro-5-hydroxy-DL-tryptophan<sup>*</sup>

Daly, J. W.; Mauger, A. B.; Yonemitsu, Osamu; Antonov, V.K.; Takase, Kazuma; Witkop, Bernhard

doi:10.1021/bi00855a002

Cited by 11 publications

(4 citation statements)

References 13 publications

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“…To further substantiate this role of the indole, the electrophilic aromatic substitution can be eliminated by reducing the pyrrole ring double bond. Accordingly, tryptophan 69 was converted to dihydrotryptophan (Scheme ) . This material underwent bis-carbamoylation to give the precursor 76 .…”

Section: Resultsmentioning

confidence: 99%

An Efficient Synthesis ofN-Methyl Amino Acids by Way of Intermediate 5-Oxazolidinones

et al. 2003

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N-Methyl amino acids occur in many natural products. Experimental strategies are presented for a unified approach to the synthesis of N-methyl derivatives through 5-oxazolidinones of the 20 common l-amino acids. The amino acids with reactive side chains that required protecting groups or devoted syntheses for side chain construction for N-methylation to proceed included serine, threonine, tyrosine, cysteine, methionine, tryptophan, asparagine, histidine, and arginine. The studies have provided improved methods for the preparation of N-methyl serine, threonine, and tyrosine. All 20 of the common l-amino acids are now available in suitable forms for solid or solution-phase peptide synthesis.

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Section: Resultsmentioning

confidence: 99%

An Efficient Synthesis ofN-Methyl Amino Acids by Way of Intermediate 5-Oxazolidinones

et al. 2003

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“…Oxytryptamine (2-oxo-2,3-dihydrotryptamine) was prepared by reaction of tryptamine hydrochloride with dimethyl sulfoxide and 12 N HC1 (Szabo-Pustav & Szabo, 1979). 2,3-Dihydro-L-tryptophan was a generous gift of Dr. John W. Daly (Daly et al, 1967). 3H20 (specific activity 25 mCi/g) was obtained from New England Nuclear.…”

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confidence: 99%

Interactions of tryptophan synthase, tryptophanase, and pyridoxal phosphate with oxindolyl-L-alanine and 2,3-dihydro-L-tryptophan: support for an indolenine intermediate in tryptophan metabolism

Phillips¹,

Miles²,

Cohen³

1984

Biochemistry

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We have examined the interaction of tryptophan synthase and tryptophanase with the tryptophan analogues oxindolyl-L-alanine and 2,3-dihydro-L-tryptophan. Since these analogues have tetrahedral geometry at carbon 3 of the heterocyclic ring, they are structurally similar to the indolenine tautomer of L-tryptophan, a proposed intermediate in reactions of L-tryptophan. Oxindolyl-L-alanine and 2,3-dihydro-L-tryptophan are potent competitive inhibitors of both tryptophan synthase and tryptophanase, with KI values (3-17 microM) 10-100-fold lower than the corresponding Km or KI values for L-tryptophan. Addition of oxindolyl-L-alanine or 2,3-dihydro-L-tryptophan to solutions of the alpha 2 beta 2 complex of tryptophan synthase results in new absorption bands at 480 or 494 nm, respectively, which are ascribed to a quinonoid or alpha-carbanion intermediate. Spectrophotometric titration data give half-saturation values of 5 and 25 microM, which are comparable to the KI values obtained in kinetic experiments. Our finding that both enzymes catalyze incorporation of tritium from 3H2O into oxindolyl-L-alanine is evidence that both enzymes form alpha-carbanion intermediates with oxindolyl-L-alanine. These results support the proposal that the indolenine tautomer of L-tryptophan is an intermediate in reactions catalyzed by both tryptophanase and tryptophan synthase. In addition, we have found that oxindolyl-L-alanine reacts irreversibly with free pyridoxal phosphate to form a covalent adduct.

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“…To facilitate the formation of the amide, the nucleophilicity of the heterocyclic nitrogen center was increased by the reduction of the aromatic indole system to indoline (Scheme ). Thus, catalytic hydrogenation of the indole double bond followed by acylation with cis -3-iodoacryloyl chloride in the presence of 2,6-lutidine gave the amide 38 . Palladium-mediated coupling 33 with trimethylsilylacetylene afforded the enyne system 39 in 78% yield for the three steps.…”

Section: The Ab → Abcd → Abcde → Abcdef Approach To 1: Successful St...mentioning

confidence: 99%

Approaches to the Synthesis of (±)-Strychnine via the Cobalt-Mediated [2 + 2 + 2] Cycloaddition: Rapid Assembly of a Classic Framework

et al. 2001

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Five synthetic approaches to racemic strychnine (1), with the cobalt-mediated [2 + 2 + 2] cycloaddition of alkynes to indoles as the key step, are described. These include the generation and attempted cyclization of macrocycle 8 and the synthesis of dihydrocarbazoles 15, 22, and 26 and their elaboration to pentacyclic structures via a conjugate addition, dipolar cycloaddition, and propellane-to-spirofused skeletal rearrangement, respectively. Finally, the successful total synthesis of 1 is discussed. The development of a short, highly convergent route (14 steps in the longest linear sequence) is highlighted by the cyclization of enynoylindole 40 with acetylene and the formal intramolecular 1,8-conjugate addition of amine 49 to form pentacycle 50. Numerous attempts toward the formation of the piperidine ring of 1 from vinyl iodide 56 were made and its successful formation via palladium-, nickel-, and radical-mediated processes is described.

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The Synthesis and Metabolism of 2,3-Dihydro-L-tryptophan and 2,3-Dihydro-5-hydroxy-DL-tryptophan^*

Cited by 11 publications

References 13 publications

An Efficient Synthesis ofN-Methyl Amino Acids by Way of Intermediate 5-Oxazolidinones

An Efficient Synthesis ofN-Methyl Amino Acids by Way of Intermediate 5-Oxazolidinones

Interactions of tryptophan synthase, tryptophanase, and pyridoxal phosphate with oxindolyl-L-alanine and 2,3-dihydro-L-tryptophan: support for an indolenine intermediate in tryptophan metabolism

Approaches to the Synthesis of (±)-Strychnine via the Cobalt-Mediated [2 + 2 + 2] Cycloaddition: Rapid Assembly of a Classic Framework

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The Synthesis and Metabolism of 2,3-Dihydro-L-tryptophan and 2,3-Dihydro-5-hydroxy-DL-tryptophan*

Cited by 11 publications

References 13 publications

An Efficient Synthesis ofN-Methyl Amino Acids by Way of Intermediate 5-Oxazolidinones

An Efficient Synthesis ofN-Methyl Amino Acids by Way of Intermediate 5-Oxazolidinones

Interactions of tryptophan synthase, tryptophanase, and pyridoxal phosphate with oxindolyl-L-alanine and 2,3-dihydro-L-tryptophan: support for an indolenine intermediate in tryptophan metabolism

Approaches to the Synthesis of (±)-Strychnine via the Cobalt-Mediated [2 + 2 + 2] Cycloaddition: Rapid Assembly of a Classic Framework

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The Synthesis and Metabolism of 2,3-Dihydro-L-tryptophan and 2,3-Dihydro-5-hydroxy-DL-tryptophan^*