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Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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The theory of catalytically perfect enzymes was first proposed by W.J. Albery and J. R. Knowles in 1976. These enzymes catalyze biochemical reactions at high-speed. Their catalytic efficiency values range from 108-109 M-1s-1. These enzymes are also called 'diffusion-controlled' as the only rate-limiting step in the catalysis is that of the substrate diffusion into the active site. Examples include triose phosphate isomerase, fumarase, and superoxide dismutase.
 
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The conversion of allylic alcohols into epoxides using the chiral catalyst was discovered by K. Barry Sharpless and is known as Sharpless epoxidation. The use of a chiral catalyst enables the formation of one enantiomer of the product in excess. This chiral catalyst is mainly a chiral complex of titanium tetraisopropoxide and tartrate ester (specific stereoisomer). The stereoisomer used in the chiral catalyst dictates the formation of the enantiomer of the product. In other words, the use of...
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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
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Light-driven Enzymatic Decarboxylation
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Recent developments in enantioselective photocatalysis.

Callum Prentice1, James Morrisson2, Andrew D Smith1

  • 1Organic Semiconductor Centre, EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, Fife, Scotland, KY16 9ST, United Kingdom.

Beilstein Journal of Organic Chemistry
|October 21, 2020
PubMed
Summary
This summary is machine-generated.

This review explores enantioselective photocatalysis, a key method for creating chiral molecules. It details various strategies, recent advances, and proposed mechanisms for enantioselective synthesis using light and catalysts.

Keywords:
enantioenrichmentenantionselective catalysisenantioselective photocatalysisphotocatalysisphotochemistry

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Area of Science:

  • Organic Chemistry
  • Photocatalysis
  • Asymmetric Synthesis

Background:

  • Enantioselective photocatalysis is a rapidly advancing field in synthetic chemistry.
  • It offers powerful strategies for accessing enantioenriched compounds.

Purpose of the Study:

  • To review diverse strategies for enantioselective synthesis by combining catalysis and photocatalysis.
  • To highlight recent developments and mechanistic insights in the field.
  • To guide and inspire future innovation in enantioselective photocatalysis.

Main Methods:

  • Literature review of enantioselective photocatalysis strategies.
  • Analysis of recent advancements and proposed reaction mechanisms.
  • Focus on the integration of enantioselective catalysis with photocatalysis.

Main Results:

  • Compilation of various methods for achieving enantioselective photocatalysis.
  • Discussion of the mechanistic underpinnings of different strategies.
  • Identification of the scope and limitations of current approaches.

Conclusions:

  • Enantioselective photocatalysis provides versatile routes to chiral molecules.
  • Understanding mechanisms is crucial for developing new synthetic methodologies.
  • This review serves as a guide for future research in the field.