- Visible-Light Mediated Tryptophan Modification in Oligopeptides Employing Acylsilanes
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A method for the selective tryptophan modification and labelling of tryptophan-containing peptides is described. Photoirradiation of acylsilanes generates reactive siloxycarbenes which undergo H?N-insertion into the indole moiety of tryptophan to give stable silyl protected hemiaminals. This method is successfully applied to chemically modify various tryptophan containing oligopeptides. The method enables the selective introduction of alkynes to peptides that are eligible for further alkyne-azide click chemistry. In addition, the dansyl fluorophore can be conjugated to a peptide using this approach.
- Reimler, Jannik,Studer, Armido
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supporting information
p. 15392 - 15395
(2021/10/04)
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- Ruthenium-Catalyzed Brook Rearrangement Involved Domino Sequence Enabled by Acylsilane-Aldehyde Corporation
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A ruthenium-catalyzed [1,2]-Brook rearrangement involved domino sequence is presented to prepare highly functionalized silyloxy indenes with atomic- and step-economy. This domino reaction is triggered by acylsilane-directed C-H activation, and the aldehyde controlled the subsequent enol cyclization/Brook Rearrangement other than β-H elimination. The protocol tolerates a broad substitution pattern, and the further synthetic elaboration of silyloxy indenes allows access to a diverse range of interesting indene and indanone derivatives.
- Lu, Xiunan,Zhang, Jian,Xu, Liangyao,Shen, Wenzhou,Yu, Feifei,Ding, Liyuan,Zhong, Guofu
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p. 5610 - 5616
(2020/07/24)
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- Tertiary α-Silyl Alcohols by Diastereoselective Coupling of 1,3-Dienes and Acylsilanes Initiated by Enantioselective Copper-Catalyzed Borylation
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An efficient synthesis of functionalized tertiary α-silyl alcohols by an enantio- and diastereoselective copper-catalyzed three-component coupling of 1,3-dienes, bis(pinacolato)diboron, and acylsilanes is reported. The reaction proceeds well with different 1,3-dienes and a broad range of aryl- as well as alkenyl- but also alkyl-substituted acylsilanes. The target compounds are formed with high regio-, diastereo-, and enantioselectivity (up to 99 % ee and d.r. >20:1) and are highly versatile synthetic building blocks.
- Feng, Jian-Jun,Oestreich, Martin
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p. 8211 - 8215
(2019/05/27)
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- Enantioselective Synthesis of Chiral 3-Substituted-3-silylpropionic Esters via Rhodium/Bisphosphine-Thiourea-Catalyzed Asymmetric Hydrogenation
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We have successfully developed the asymmetric hydrogenation of β-silyl-α,β-unsaturated esters to prepare chiral 3-substituted-3-silylpropionic ester products catalyzed by rhodium/bisphosphine-thiourea (ZhaoPhos) with excellent results (up to 97% yield, >99% ee, 1500 TON). Moreover, our hydrogenation products can be efficiently converted to other important organic molecules, such as chiral ethyl (R)-3-hydroxy-3-phenylpropanoate or (R)-3-[dimethyl(phenyl)silyl]-3-phenylpropanoic acid. (Figure presented.).
- Zhang, Zongpeng,Han, Zhengyu,Gu, Guoxian,Dong, Xiu-Qin,Zhang, Xumu
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p. 2585 - 2589
(2017/08/16)
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- Silver(i)-promoted insertion into X-H (X = Si, Sn, and Ge) bonds with N-nosylhydrazones
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Silver(i)-promoted carbene insertion into X-H (X = Si, Sn, and Ge) bonds has been realized by using unstable diazo compounds, which are generated in situ from N-nosylhydrazones as carbene precursors. The reaction tolerates a wide range of functional groups and delivers a number of valuable silicon-containing compounds in very high yields (up to 96%). Moreover, organostannanes and organogermanes were as well effectively obtained in very good yields under optimal conditions.
- Liu, Zhaohong,Li, Qiangqiang,Yang, Yang,Bi, Xihe
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p. 2503 - 2506
(2017/03/08)
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- Oxidative [1,2]-Brook Rearrangements Exploiting Single-Electron Transfer: Photoredox-Catalyzed Alkylations and Arylations
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Oxidative [1,2]-Brook rearrangements via hypervalent silicon intermediates induced by photoredox-catalyzed single-electron transfer have been achieved, permitting the formation of reactive radical species that can engage in alkylations and arylations.
- Deng, Yifan,Liu, Qi,Smith, Amos B.
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supporting information
p. 9487 - 9490
(2017/07/24)
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- Intermolecular Schmidt reaction of alkyl azides with acyl silanes
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The first intermolecular Schmidt reaction of alkyl azides with acyl silanes has been designed and realized, producing a range of amides with absolute site selectivity in good to excellent yields. The mechanism of the conversion has been proposed, and the reaction exhibits scope of substrates.
- Yu, Chun-Jiao,Li, Rui,Gu, Peiming
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supporting information
p. 3568 - 3570
(2016/07/18)
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- Synthesis of Optically Pure Arylsilylcarbinols and Their Use as Chiral Auxiliaries in Oxacarbenium Ion Reactions
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A family of arylsilylcarbinols was synthesized and investigated as chiral auxiliaries for oxacarbenium ion reactions. The optically pure arylsilylcarbinols were prepared using Noyori's transfer hydrogenation catalyst 11. The transfer hydrogenation shows very good enantioselectivities and turnover efficiency for the aryl silyl ketones and is the method of choice for preparing these optically pure alcohols. The diastereoselective addition of allyltrimethylsilane to an in situ generated oxacarbenium ion was explored using Marko's conditions. The selectivity for a representative aliphatic aldehyde was very good, but the selectivity was significantly reduced with unsaturated and aromatic aldehydes. The range of selectivities with different auxiliaries was narrow, and the most practical auxiliary is the phenylsilylcarbinol 2.
- Huckins, John R.,Rychnovsky, Scott D.
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p. 10135 - 10145
(2007/10/03)
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- Tandem carbon-carbon bond constructions via catalyzed cyanation/Brook rearrangement/C-acylation reactions of acylsilanes
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(equation presented) A tandem nucleophile-catalyzed cyanation/Brook rearrangement/C-acylation has been developed. Phase transfer cocatalysts facilitate cyanide-catalyzed reactions between acylsilanes and cyanoformates to afford protected tertiary carbinol
- Linghu, Xin,Nicewicz, David A.,Johnson, Jeffrey S.
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p. 2957 - 2960
(2007/10/03)
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