- Correction to: Nickel-catalyzed enantioselective reductive cross-coupling of styrenyl aziridines (Journal of the American Chemical Society (2017) 139 (5688-5691) DOI: 10.1021/jacs.7b03448)
-
Table of Contents. The enantiomer of the BiOx ligand that delivers the indicated absolute configuration of product is (R,R)-(4-heptyl)BiOx. The corrected graphic is shown below: Page 5690. The absolute configuration of ligand L7 (4-heptyl- BiOx) was misas
- Woods, Brian P.,Orlandi, Manuel,Huang, Chung-Yang Dennis,Sigman, Matthew S.,Doyle, Abigail G.
-
supporting information
p. 7744 - 7745
(2018/06/26)
-
- Nickel-Catalyzed Enantioselective Reductive Cross-Coupling of Styrenyl Aziridines
-
A Ni-catalyzed reductive cross-coupling of styrenyl aziridines with aryl iodides is reported. This reaction proceeds by a stereoconvergent mechanism and is thus amenable to asymmetric catalysis using a chiral bioxazoline ligand for Ni. The process allows
- Woods, Brian P.,Orlandi, Manuel,Huang, Chung-Yang,Sigman, Matthew S.,Doyle, Abigail G.
-
supporting information
p. 5688 - 5691
(2017/05/04)
-
- Asymmetric synthesis of propargylamines as amino acid surrogates in peptidomimetics
-
The amide moiety of peptides can be replaced for example by a triazole moiety, which is considered to be bioisosteric. Therefore, the carbonyl moiety of an amino acid has to be replaced by an alkyne in order to provide a precursor of such peptidomimetics. As most amino acids have a chiral center at Cα, such amide bond surrogates need a chiral moiety. Here the asymmetric synthesis of a set of 24 N-sulfinyl propargylamines is presented. The condensation of various aldehydes with Ellman's chiral sulfinamide provides chiral N-sulfinylimines, which were reacted with (trimethylsilyl)ethynyllithium to afford diastereomerically pure N-sulfinyl propargylamines. Diverse functional groups present in the propargylic position resemble the side chain present at the Cα of amino acids. Whereas propargylamines with (cyclo)alkyl substituents can be prepared in a direct manner, residues with polar functional groups require suitable protective groups. The presence of particular functional groups in the side chain in some cases leads to remarkable side reactions of the alkyne moiety. Thus, electron-withdrawing substituents in the Cα-position facilitate a base induced rearrangement to α,β-unsaturated imines, while azide-substituted propargylamines form triazoles under surprisingly mild conditions. A panel of propargylamines bearing fluoro or chloro substituents, polar functional groups, or basic and acidic functional groups is accessible for the use as precursors of peptidomimetics.
- Wünsch, Matthias,Schr?der, David,Fr?hr, Tanja,Teichmann, Lisa,Hedwig, Sebastian,Janson, Nils,Belu, Clara,Simon, Jasmin,Heidemeyer, Shari,Holtkamp, Philipp,Rudlof, Jens,Klemme, Lennard,Hinzmann, Alessa,Neumann, Beate,Stammler, Hans-Georg,Sewald, Norbert
-
supporting information
p. 2428 - 2441
(2017/12/06)
-
- Asymmetric vinylogous Mannich reactions: A versatile approach to functionalized heterocycles
-
Asymmetric vinylogous Mannich reaction (VMR) of 2-(tert- butyldimethylsilyloxy)furan (TBSOF, 1) with (RS)- or (S S)-t-BS-imines (3) furnished 5-aminoalkylbutenolides 7a-k in 75-87% yields with anti/syn ratios ranging from 75:25 to 97:3. Butenolides 7a-f,k were readily converted into substituted lactones 8 and 5 and 6-substituted 5-hydroxypiperidin-2-ones 11a-g, which are, in turn, key intermediates for the synthesis of many bioactive compounds.
- Ruan, Shu-Tang,Luo, Jie-Min,Du, Yu,Huang, Pei-Qiang
-
supporting information; experimental part
p. 4938 - 4941
(2011/11/06)
-
- Further studies toward the stereocontrolled synthesis of silicon-containing peptide mimics
-
Further studies are reported on the utilization of the versatile reaction between chiral sulfinimines and alkyldiphenylsilyl lithium reagents with the goal of preparing a wide range of silanediol-based protease inhibitors. In particular, focus has been placed to demonstrate how a number of genetically encoded amino acid side chains such as serine, threonine, tyrosine, lysine, proline, arginine, aspartate and asparagine might be incorporated into the overall approach. Efforts to apply this synthetic methodology for accessing biologically relevant silanediol dipeptide mimics are also described. This includes the synthesis of a potential inhibitor of the human neutrophil elastase, as well as a diphenylsilane mimic of a hexapeptide fragment of the human islet amyloid polypeptide.
- Hernandez, Dacil,Lindsay, Karl B.,Nielsen, Lone,Mittag, Tina,Bjerglund, Klaus,Friis, Stig,Mose, Rasmus,Skrydstrup, Troels
-
supporting information; experimental part
p. 3283 - 3293
(2010/08/07)
-
- Asymmetric synthesis of protected 1,2-amino alcohols using tert-butanesulfinyl aldimines and ketimines
-
tert-Butanesulfinyl aldimines and ketimines bearing an α-benzyloxy or α-silyloxy substituent serve as precursors in the synthesis of protected 1,2-amino alcohols in high yields and diastereoselectivities. General protocols are described for the addition of unbranched alkyl, branched alkyl, and aryl organometallic reagents to N-sulfinyl aldimines 1 and 2 and ketimines 5 and 6. Furthermore, the selective N- or O-deprotection of sulfinamide products 3, 4, 7, and 8 is described, enabling further synthetic transformations of the reaction products.
- Tang,Volkman,Ellman
-
p. 8772 - 8778
(2007/10/03)
-
- A facile three-step synthesis of 1,2-amino alcohols using the Ellman homochiral tert-butylsulfinamide
-
Addition of organometallic reagents to tert-butylsulfinimines derived from tert-butyldimethylsiloxyacetaldehyde stereoselectively generates protected 1,2-amino alcohols. Removal of the acid labile protecting groups affords amino alcohols in high yield. The predominant diastereomer is opposite to that predicted by the traditional Ellman model; therefore, a chelation model invoking rapid E/Z isomerization of the imine is proposed to rationalize the observed selectivity.
- Barrow, James C.,Ngo, Phung L.,Pellicore, Janetta M.,Selnick, Harold G.,Nantermet, Philippe G.
-
p. 2051 - 2054
(2007/10/03)
-