Synthesis of silicon containing alanines

Sibi, Mukund P.; Harris, Brant J.; Shay, John J.; Hajra, Saumen

doi:10.1016/s0040-4020(98)00356-1

Cited by 25 publications

(16 citation statements)

References 25 publications

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“…[13] In this case, TMS-Ala is prepared in both enantiomeric forms by asymmetric synthesis starting from Schöllkopf's reagent and chloromethyltrimethylsilane. Other syntheses of TMS-Ala have been described in the literature, [14][15][16] and a more recent report concerns γ-silylated amino acids. [17] To the best of our knowledge, the other well-known methods for asymmetric synthesis of amino acids (Williams, [18] Oppolzer, [19] hydroxypinanone [20] methods) have not been applied to silicon-containing amino acids.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Silaproline, a New Proline Surrogate

Vivet¹,

Cavelier

Martinez

2000

Eur. J. Org. Chem.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Silaproline, a New Proline Surrogate

Vivet¹,

Cavelier

Martinez

2000

Eur. J. Org. Chem.

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“…Treatment of a-bromo glycine derivative 35 with an excess of (phenyldimethylsilyl)methyl magnesium chloride initiates dehydrohalogenation and then traps the imine 36 to give the racemic, protected amino acid derivative 37 (Scheme 6.5) [23]. Disconnection D has been described by Sibi et al [24], using a silyl cuprate. The optically active iodomethyloxazolidinone 38 undergoes nucleophilic displacement of the iodide with dimethylphenylsilyl lithium and Cu(I) cyanide to install the silicon.…”

Section: Synthesis Of B-silylalanine and Derivativesmentioning

confidence: 99%

“…The optically active iodomethyloxazolidinone 38 undergoes nucleophilic displacement of the iodide with dimethylphenylsilyl lithium and Cu(I) cyanide to install the silicon. Boc-derivatization of the nitrogen, hydrolysis of the heterocycle, and oxidation of the primary alcohol gave the dimethylphenylsilylalanine in Boc-protected form 40 (Scheme 6.6) [24].…”

Section: Synthesis Of B-silylalanine and Derivativesmentioning

confidence: 99%

Chemistry of Silicon‐Containing Amino Acids

Sieburth

2009

Amino Acids, Peptides and Proteins in Organic Chemistry

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“…Apart from resolution or dynamic resolution of racemic mixtures [3] [5 ± 7], several stereoselective syntheses have been performed. In these syntheses, either the Si-containing side chains were introduced by diastereoselective alkylation of chiral glycine anion synthons [3] [8 ± 10] or by b-substitution of serine derivatives [11]. Alternatively, the amino acids were prepared by stereoselective a-amination of bsilylated carboxylic acids [7] [12].…”

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“…C-NMR: 177.2 (s, COOH); 58.8 (d, N 3 CH); 41.1 (t, N 3 CH 2 ); 17.0 (t, SiCH 2 ); À 4.0, À 4.1 (q, Me 2 Si). CI-MS: 190(11), 189 (93, [M NH 4 À CH 2 N 3 À H] ), 149(11), 148 (100, [M NH 4 À CH 2 N 3 À N 3 ] ), 144(11), 131(11), 92(10), 91(8). Anal.…”

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Towards Functionalized Silicon‐Containing α‐Amino Acids: Asymmetric Syntheses of Sila Analogs of Homoserine and Homomethionine

Smith

Bienz

2004

Helvetica Chimica Acta

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Dedicated to Dr. G¸nther Ohloff on the occasion of his 80th birthdayThe homoserine and homomethionine sila analogs, (R)-HOSi(Me 2 )CH 2 CH(NH 2 )CO 2 H ((R)-21) and (R)-MeSCH 2 Si(Me 2 )CH 2 CH(NH 2 )CO 2 H ((R)-24), respectively, were each synthesized in nine steps and in 30 and 23% overall yield, respectively, from commercially available ClSiMe 2 CH 2 Cl. The key step of both syntheses was the asymmetric a-bromination of an Evans amide to introduce the stereogenic center of the amino acids with defined absolute configuration. While the preparation of the homomethionine analog (R)-24 followed the expected pathway, the sila analog of homoserine, (R)-21, was unexpectedly formed during the catalytic hydrogenation of an N 3 CH 2 -substituted silane derivative.Introduction. ± Nonproteinogenic and unnatural amino acids are important building blocks for peptide chemistry [1 ± 3], and, among such compounds, sila amino acids are of increasing interest [3 ± 13]. With their large hydrophobic groups, they are expected and have been shown to offer several advantages over classical amino acids when incorporated into peptides, such as prevention of hydrophobic-pocket collapse, higher lipophilicity, and enhanced stability towards proteolytic enzymatic degradation Alternatively, the amino acids were prepared by stereoselective a-amination of bsilylated carboxylic acids [7] [12]. While most of the previous studies targeted rather simple trialkyl-or trialkyl/triarylsilanes, Tacke et al. reported the first enantioselective synthesis of Si-containing amino acids that are hetero-functionalized at a Si-containing side chain [10]. However, the hetero group, an amino function, was introduced early in the synthetic scheme, limiting the versatility of the method. In continuation of our investigations [6] [7] [13], we were looking for a more flexible route to functionalized sila amino acids, considering halogenomethyl-substituted silanes such as 4 as precursors.

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Synthesis of silicon containing alanines

Cited by 25 publications

References 25 publications

Synthesis of Silaproline, a New Proline Surrogate

Synthesis of Silaproline, a New Proline Surrogate

Chemistry of Silicon‐Containing Amino Acids

Towards Functionalized Silicon‐Containing α‐Amino Acids: Asymmetric Syntheses of Sila Analogs of Homoserine and Homomethionine

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