scholarly journals Enantioselective Hydroalkylation of α,β-Unsaturated Amides through Reversed syn-Hydrometallation of NiH

Author(s):  
Fang Zhou ◽  
Shaolin Zhu

Enantioselective synthesis of a wide range of structurally diverse <a>β</a>-chiral amides has been achieved through nickel-catalyzed regio-reversed hydroalkylation of α,β-unsaturated amides with alkyl iodides in the presence of a hydrosilane. Different from the classical homolysis/enantioconvergent recombination process of Ni(III) intermediates as the enantio-determining step, chiral induction in this reductive hydroalkylation was achieved through an enantiodifferentiating regio-reversed <i>syn</i>-hydrometallation process of α,β-unsaturated amides.

2021 ◽  
Author(s):  
Fang Zhou ◽  
Shaolin Zhu

Enantioselective synthesis of a wide range of structurally diverse <a>β</a>-chiral amides has been achieved through nickel-catalyzed regio-reversed hydroalkylation of α,β-unsaturated amides with alkyl iodides in the presence of a hydrosilane. Different from the classical homolysis/enantioconvergent recombination process of Ni(III) intermediates as the enantio-determining step, chiral induction in this reductive hydroalkylation was achieved through an enantiodifferentiating regio-reversed <i>syn</i>-hydrometallation process of α,β-unsaturated amides.


2008 ◽  
Vol 14 (34) ◽  
pp. 10564-10568 ◽  
Author(s):  
José Lorenzo Alonso-Gómez ◽  
Patrick Schanen ◽  
Pablo Rivera-Fuentes ◽  
Paul Seiler ◽  
François Diederich

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Qiupeng Peng ◽  
Bingjia Yan ◽  
Fangyi Li ◽  
Ming Lang ◽  
Bei Zhang ◽  
...  

AbstractAlthough utilization of fluorine compounds has a long history, synthesis of chiral fluorinated amino acid derivatives with structural diversity and high stereoselectivity is still very appealing and challenging. Here, we report a biomimetic study of enantioselective [1,3]-proton shift of β,β-difluoro-α-imine amides catalyzed by chiral quinine derivatives. A wide range of corresponding β,β-difluoro-α-amino amides were achieved in good yields with high enantioselectivities. The optically pure β,β-difluoro-α-amino acid derivatives were further obtained, which have high application values in the synthesis of fluoro peptides, fluoro amino alcohols and other valuable fluorine-containing molecules.


2020 ◽  
Author(s):  
Deyun Qian ◽  
Srikrishna Bera ◽  
Xile Hu

Chiral alkyl amines are omnipresent as bio-active molecules and synthetic intermediates. Catalytic and enantioselective synthesis of alkyl amines from readily accessible precursors is challenging. Here we develop a nickel-catalyzed hydroalkylation method to assemble a wide range of chiral alkyl amines from enamides and alkyl halides in high regio- and enantioselectivity. The method works for both non-activated and activated alkyl halides, and is able to produce enantiomerically enriched amines with two minimally differentiated alpha-alkyl substituents. The mild conditions lead to high functional group tolerance, which is demonstrated in the post-product functionalization of many natural products and drug molecules, as well as the synthesis of chiral building blocks and key intermediates to bio-active compounds.


2020 ◽  
Author(s):  
Deyun Qian ◽  
Srikrishna Bera ◽  
Xile Hu

Chiral alkyl amines are omnipresent as bio-active molecules and synthetic intermediates. Catalytic and enantioselective synthesis of alkyl amines from readily accessible precursors is challenging. Here we develop a nickel-catalyzed hydroalkylation method to assemble a wide range of chiral alkyl amines from enamides and alkyl halides in high regio- and enantioselectivity. The method works for both non-activated and activated alkyl halides, and is able to produce enantiomerically enriched amines with two minimally differentiated alpha-alkyl substituents. The mild conditions lead to high functional group tolerance, which is demonstrated in the post-product functionalization of many natural products and drug molecules, as well as the synthesis of chiral building blocks and key intermediates to bio-active compounds.


2020 ◽  
Author(s):  
Nicolas Duchemin ◽  
Martin Cattoen ◽  
Oscar Gayraud ◽  
Silvia Anselmi ◽  
Bilal Siddiq ◽  
...  

A highly enantioselective synthesis of a-branched acrylonitriles is reported featuring a one-pot sequential asymmetric Michael addition/retro-Dieckmann/retro-Michael fragmentation cascade. The method, which relies on a solid, bench-stable and commercially available acrylonitrile surrogate, is practical, scalable, highly versatile, and provides a direct access to a wide range of enantioenriched nitrile-containing building blocks. Most importantly, the method offers a new tool to incorporate an acrylonitrile moiety in an asymmetric fashion.<br>


Author(s):  
Nicolas Duchemin ◽  
Martin Cattoen ◽  
Oscar Gayraud ◽  
Silvia Anselmi ◽  
Bilal Siddiq ◽  
...  

A highly enantioselective synthesis of α-branched acrylonitriles is reported featuring an unprecedented formal cross Rauhut-Currier reaction consisting of an asymmetric Michael addition/retro-Dieckmann/retro-Michael fragmentation cascade. The method, which involves the use of an acrylonitrile surrogate, is practical, scalable and highly versatile, and provides a straightforward access to a wide range of enantioenriched nitrile-containing building blocks without using acrylonitrile or any source of cyanide. Most importantly, it offers a new tool to incorporate an acrylonitrile moiety in an asymmetric fashion.<br>


2017 ◽  
Vol 2 (34) ◽  
pp. 11240-11243
Author(s):  
Ruiquan Liu ◽  
Lei Wang ◽  
Qibo Li ◽  
Min Liao ◽  
Zhikun Yang ◽  
...  

Author(s):  
R.W. Horne

The technique of surrounding virus particles with a neutralised electron dense stain was described at the Fourth International Congress on Electron Microscopy, Berlin 1958 (see Home & Brenner, 1960, p. 625). For many years the negative staining technique in one form or another, has been applied to a wide range of biological materials. However, the full potential of the method has only recently been explored following the development and applications of optical diffraction and computer image analytical techniques to electron micrographs (cf. De Hosier & Klug, 1968; Markham 1968; Crowther et al., 1970; Home & Markham, 1973; Klug & Berger, 1974; Crowther & Klug, 1975). These image processing procedures have allowed a more precise and quantitative approach to be made concerning the interpretation, measurement and reconstruction of repeating features in certain biological systems.


Author(s):  
E.D. Wolf

Most microelectronics devices and circuits operate faster, consume less power, execute more functions and cost less per circuit function when the feature-sizes internal to the devices and circuits are made smaller. This is part of the stimulus for the Very High-Speed Integrated Circuits (VHSIC) program. There is also a need for smaller, more sensitive sensors in a wide range of disciplines that includes electrochemistry, neurophysiology and ultra-high pressure solid state research. There is often fundamental new science (and sometimes new technology) to be revealed (and used) when a basic parameter such as size is extended to new dimensions, as is evident at the two extremes of smallness and largeness, high energy particle physics and cosmology, respectively. However, there is also a very important intermediate domain of size that spans from the diameter of a small cluster of atoms up to near one micrometer which may also have just as profound effects on society as “big” physics.


Sign in / Sign up

Export Citation Format

Share Document