ChemInform Abstract: Amino Acids as Chiral Building Blocks: Dihydrothiazole Derivatives (δ4‐Thiazoline) Made from Cysteine.

Seebàch, Dieter; Jeanguenat, André; Schmidt, Johannes; Maetzke, Thomas

doi:10.1002/chin.199015156

ChemInform

1990

DOI: 10.1002/chin.199015156

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ChemInform Abstract: Amino Acids as Chiral Building Blocks: Dihydrothiazole Derivatives (δ4‐Thiazoline) Made from Cysteine.

Dieter Seebàch

André Jeanguenat

Johannes Schmidt

et al.

Abstract: Pivalaldehyde (I) reacts with L‐cysteine hydrochloride (II) to give the 1,3‐thiazolidinium chloride (III) which is N‐acylated with benzyl chloroformate (IV) to give (V).

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“…In previous work, it was found that 1 :I cisltrans-mixtures of N-unsubstituted oxazolidines give preferentially the cis-products upon formylation and methoxycarbonylation [ 1 11 [ 141 [33]. Similarly, thiazolidines derived from cysteine were found to give exclusively the cis -products upon benzyloxycarbonylation [34]. The structural information from X-ray analyses was used to interpret this stereoselectivity [ 1 813).…”

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confidence: 94%

Preparation of Oxazolidine‐Containing Peptides: Unusual effects in Rh^III‐catalyzed acetalizations of aldehydes with urethane‐protected serine and threonine esters and with dipeptides containing serine or threonine residues at the N‐terminus

Seebàch¹,

Sommerfeld²,

Jiang³

et al. 1994

Helvetica Chimica Acta

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The cyclization reaction of aldehydes with Z-and Boc-protectedB -hydroxyamino-acid esters (Tables 1 and 2), or of dipeptides containing serine or threonine at the N-terminus (Table 3), to give oxazolidine derivatives, occurs in the presence of isopropyl orthoformate and catalytic amounts of [Rh(MeCN)3(triphos)](CF3S03)3. The reaction may be carried out under kinetic or under thermodynamic control, so that the ratio of the two possible epimeric products can be changed. The protecting group can be removed from the 3-position of the oxazolidine ring, and the resulting NH group can be coupled with another amino acid. Thus, a new method for the preparation of peptides containing B -hydroxy-amino acid-derived oxazolidines ('pseudo-prolines') is available. N-Neopentyl-substituted tripeptides are also described.Serine-Derived Oxazolidines and Transition-Metal Acetalization Catalysts. -Oxazolidines, prepared from the j3 -hydroxyamino acids serine and threonine, have found multiple uses in stereoselective syntheses [l-lo]. They have been employed by one of our groups to synthesize a-branched analogs of serine and threonine, as well as other synthetically interesting building blocks [ 1 1-14], applying the principle of self-regeneration of stereogenic centers [15-171. Not only have these amino acids shown themselves as useful building blocks in diastereoselective syntheses, but the concomitant mechanistic and structural investigations have led to better understanding of the role amide groups play in modern organic synthesis, as discussed in a recently published review article [18]. Following a totally different line of work, Mutter et al. showed that the solubility problems often encountered both in solid and solution-phase peptide synthesis can be overcome by incorporating serines, as oxazolidine derivatives ('pseudo-prolines'), thus preventing the formation of poorly solublej3 -strands [ 191. For this purpose, the pivalaldehyde acetal of serine methyl ester was used as a building block in an otherwise conventional peptide synthesis.Recent work on transition-metal-catalyzed acetalization indicated that it might be possible to obtain oxazolidines directly from a given peptide. For over a decade, a ') Part of the projected Ph. D. theses of T. S. and of J. Q., ETH-Zurich. The authors gratefully acknowledge a stipend given to T. S. by the Verband der Chemisehen Industrrr (D-Frankfurt).

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mentioning

confidence: 94%

Preparation of Oxazolidine‐Containing Peptides: Unusual effects in Rh^III‐catalyzed acetalizations of aldehydes with urethane‐protected serine and threonine esters and with dipeptides containing serine or threonine residues at the N‐terminus

Seebàch¹,

Sommerfeld²,

Jiang³

et al. 1994

Helvetica Chimica Acta

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“…Nongenetically coded amino acids, particularly non-natural α-amino acids, have contributed strongly in the area of peptide research. These amino acids play a significant role in peptide analogues to limit conformational flexibility, to enhance enzymatic stability, and to improve pharmacodynamics and bioavailability. − Side chain conformational restrictions deliver a practical approach in peptidomimetics to understand the interactions of peptides with proteins, nucleic acids, lipids, and sugars in biological systems…”

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confidence: 99%

Enantiopure Synthesis of Side Chain-Modified α-Amino Acids and 5-cis-Alkylprolines

Mohite

Bhat

2012

J. Org. Chem.

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A short, concise synthesis of enantiopure, side chain-modified α-amino acids such as 4-oxo-L-norvaline, 6-oxo-L-homonorleucine, and 5-cis-alkyl prolines is described. Knoevenagel condensation of l-aminocarboxylate-derived β-ketoesters with aldehydes followed by reductive decarboxylation results in unnatural α-amino acids in good yield. A fluorescent amino acid is synthesized using a similar protocol. These studies show that aminocarboxylate-derived β-ketoesters are very useful intermediates and the method employed is both general and practical for the preparation of γ(δ)-oxo α-amino acids and alkylprolines.

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“…

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The X-ray structures of fifteen 1,3-imidazolidine, 1,3-oxazolidine, 1,3-dioxan-4-one, and hydropyrimidine-4( I H)-one derivatives are described ( Table 2) and compared with known structures of similar compounds (Figs. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. The differences between structures containing exocyclic N-acyl groups and those lacking this structural element arise from the A',' effect of the amide moieties.

…”

mentioning

confidence: 99%

ChemInform Abstract: Structure and Reactivity of Five‐ and Six‐Ring N,N‐, N,O‐, and O,O‐ Acetals: A Lesson in Allylic 1,3‐Strain (A1,3 Strain).

et al. 1992

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~~~~The X-ray structures of fifteen 1,3-imidazolidine, 1,3-oxazolidine, 1,3-dioxan-4-one, and hydropyrimidine-4( I H)-one derivatives are described (Table 2) and compared with known structures of similar compounds (Figs. 1-20). The differences between structures containing exocyclic N-acyl groups and those lacking this structural element arise from the A',' effect of the amide moieties. Even I-Bu groups are forced into axial positions of six-ring half-chair or into flag-pole positions of six-ring twist-boat conformers by this effect (Figs. 16-20). In the N-acylated five-membered heterocycles, a combination of ring strain and A',3 strain leads to strong pyramidalizations of the amide N-atoms (Table I ) such that the acyl groups wind up on one side and the other substituents on the opposite side of the rings (Figs. 4-9 and Scheme 3 ) . Thus, the acyl (protecting!) groups strongly contribute to the steric bias between the two faces of the rings. Observed, at first glance surprizing stereoselectivities of reactions of these heterocycles (Schemes I and 2 ) are interpreted (Scheme 3 ) as an indirect consequence of the amide A's3 strain effect. The conclusions drawn are considered relevant for a better understanding of the ever increasing role which amide groups play in stereoselective syntheses.

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ChemInform Abstract: Amino Acids as Chiral Building Blocks: Dihydrothiazole Derivatives (δ4‐Thiazoline) Made from Cysteine.

Abstract: Pivalaldehyde (I) reacts with L‐cysteine hydrochloride (II) to give the 1,3‐thiazolidinium chloride (III) which is N‐acylated with benzyl chloroformate (IV) to give (V).

Cited by 3 publications

References 0 publications

Preparation of Oxazolidine‐Containing Peptides: Unusual effects in Rh^III‐catalyzed acetalizations of aldehydes with urethane‐protected serine and threonine esters and with dipeptides containing serine or threonine residues at the N‐terminus

Preparation of Oxazolidine‐Containing Peptides: Unusual effects in Rh^III‐catalyzed acetalizations of aldehydes with urethane‐protected serine and threonine esters and with dipeptides containing serine or threonine residues at the N‐terminus

Enantiopure Synthesis of Side Chain-Modified α-Amino Acids and 5-cis-Alkylprolines

ChemInform Abstract: Structure and Reactivity of Five‐ and Six‐Ring N,N‐, N,O‐, and O,O‐ Acetals: A Lesson in Allylic 1,3‐Strain (A1,3 Strain).

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ChemInform Abstract: Amino Acids as Chiral Building Blocks: Dihydrothiazole Derivatives (δ4‐Thiazoline) Made from Cysteine.

Abstract: Pivalaldehyde (I) reacts with L‐cysteine hydrochloride (II) to give the 1,3‐thiazolidinium chloride (III) which is N‐acylated with benzyl chloroformate (IV) to give (V).

Cited by 3 publications

References 0 publications

Preparation of Oxazolidine‐Containing Peptides: Unusual effects in RhIII‐catalyzed acetalizations of aldehydes with urethane‐protected serine and threonine esters and with dipeptides containing serine or threonine residues at the N‐terminus

Preparation of Oxazolidine‐Containing Peptides: Unusual effects in RhIII‐catalyzed acetalizations of aldehydes with urethane‐protected serine and threonine esters and with dipeptides containing serine or threonine residues at the N‐terminus

Enantiopure Synthesis of Side Chain-Modified α-Amino Acids and 5-cis-Alkylprolines

ChemInform Abstract: Structure and Reactivity of Five‐ and Six‐Ring N,N‐, N,O‐, and O,O‐ Acetals: A Lesson in Allylic 1,3‐Strain (A1,3 Strain).

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Product

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Preparation of Oxazolidine‐Containing Peptides: Unusual effects in Rh^III‐catalyzed acetalizations of aldehydes with urethane‐protected serine and threonine esters and with dipeptides containing serine or threonine residues at the N‐terminus

Preparation of Oxazolidine‐Containing Peptides: Unusual effects in Rh^III‐catalyzed acetalizations of aldehydes with urethane‐protected serine and threonine esters and with dipeptides containing serine or threonine residues at the N‐terminus