Synthesis of silicon-containing α-amino acids and hydantoins

Smith, Richard J.; Bratovanov, Svetoslav; Bienz, Stefan

doi:10.1016/s0040-4020(97)00887-9

Cited by 27 publications

(17 citation statements)

References 8 publications

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“…Data of (4R,2'R)-12a: a 20 D À 40. 13 : 3085w, 3060w, 3030w, 3000w, 2960m, 2920m, 2870w, 1780s, 1705s, 1605w, 1585w, 1495w, 1480w, 1455m, 1445w, 1385s, 1350m, 1290m, 1260s, 1210s, 1200s 1 : 1, 0.29 g, 85%). Colorless oil.…”

Section: Experimental Partmentioning

confidence: 98%

“…to CHCl 3 (d 7.26), J in Hz. 13 C-NMR Spectra: in CDCl 3 ; Bruker ARX-300 (75.5 MHz); d in ppm rel. to CDCl 3 (d 77.0); multiplicities from DEPT-135 and DEPT-90 experiments; the interpretation of the NMR spectra is based on cross-correlation with a number of reference samples.…”

Section: Experimental Partmentioning

confidence: 99%

“…1 H-NMR: 5.87 (ddt, J 16.5, 10.1, 6.3, CH ); 5.01 (ddd, J 17.0, 3.5, 1.7, 1 H, CH 2 ); 4.92 (ddd, J 10.1, 3.2, 1.4, 1 H, CH 2 ); 2.79 (s, ClCH 2 ); 2.15 ± 2.06 (m, CH 2 CH ); 0.79 ± 0.73 (m, CH 2 Si); 0.12 (s, Me 2 Si). 13 C-NMR: 143.0 (d, CH ); 115.2 (t, CH 2 ); 32.3 (t, CH 2 Cl); 29.6 (t, CH 2 CH ); 14.8 (t, SiCH 2 ); À 2.5 (q, Me 2 Si). EI-MS: 113 (100, [M À CH 2 Cl] ), 107 (15, [M À C 4 H 7 ] ), 93 (14), 85 (48), 81 (26), 79 (71), 63 (18), 59 (77).…”

Section: Experimental Partmentioning

confidence: 99%

“…1 H-NMR: 2.80 (s, ClCH 2 ); 2.44 ± 2.38 (m, CH 2 CO); 1.03 ± 0.97 (m, SiCH 2 ); 0.14 (s, Me 2 Si). 13 C-NMR: 180.7 (s, CO); 29.8 (t, ClCH 2 ); 28.3 (t, CH 2 CO); 8.6 (t, SiCH 2 ); À 4.8 (q, Me 2 Si). CI-MS: 163 (11) (4).…”

Section: Experimental Partmentioning

confidence: 99%

“…After stirring at À 788 for 2 h and at 238 for 2 h, the reaction was quenched with H 2 O, and the mixture was extracted with Et 2 O and chromatographed (AcOEt/hexane 1 : 9) to give 4 (8.92 g, 84% ) 2 N); 1.42 ± 1.33 (m, CH 2 (CH 2 CH 2 ) 2 N); 1.03 ± 0.86 (m, SiCH 2 ); 0.11 (s, Me 2 Si). 13 C-NMR: 174.7 (s, CON); 153.4 (s, COO); 135.3 (s, arom. C); 129.4, 128.9 (2d, 4 arom.…”

Section: Experimental Partmentioning

confidence: 99%

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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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Section: Experimental Partmentioning

confidence: 98%

Section: Experimental Partmentioning

confidence: 99%

Section: Experimental Partmentioning

confidence: 99%

Section: Experimental Partmentioning

confidence: 99%

Section: Experimental Partmentioning

confidence: 99%

See 3 more Smart Citations

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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Synthesis of 1,2,3,4-Tetrahydroisoquinoline-3-carboxylic Acid (Tic) Derivatives by Cycloaddition Approaches

Kotha

Sreenivasachary

2001

Eur. J. Org. Chem.

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A new and general synthetic methodology for the preparation of functionalized 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid derivatives by a cycloaddition strategy is described. The synthesis of various enyne building blocks 12, 13, 21, and 22 containing an α-amino acid moiety using Schiff base 8 as a glycine equivalent has been achieved under mild reaction conditions. These building blocks have been utilized in the synthesis of inner-outer ring dienes 23 and 24 and ex-

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Enantioselective Syntheses of α‐Silyl Amines via a Copper‐N‐Heterocyclic Carbene Catalyzed Nucleophilic Silicon Transfer to Imines

et al. 2014

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We developed an efficient and enantioselective method for the synthesis of chiral α‐silyl amines. In the presence of a copper(I)‐chiral monodentate N‐heterocyclic carbene complex (5 mol %), smooth nucleophilic silicon transfer from Me2PhSiBpin (pin=pinacolato) to tosyl‐protected aldimines affords the corresponding α‐silyl amines in 77–93 % yields over 15 examples and satisfactory ee of 79–99 %. The asymmetric silylation of ketimines was also explored.

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Synthesis of silicon-containing α-amino acids and hydantoins

Cited by 27 publications

References 8 publications

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

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

Synthesis of 1,2,3,4-Tetrahydroisoquinoline-3-carboxylic Acid (Tic) Derivatives by Cycloaddition Approaches

Enantioselective Syntheses of α‐Silyl Amines via a Copper‐N‐Heterocyclic Carbene Catalyzed Nucleophilic Silicon Transfer to Imines

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