Asymmetric reactions/Enantioselective synthesis

General info: Circularly polarized photons and spin polarized electrons are the actual chiral influence.
Epoxide: An organic compound whose molecule contains a three-membered ring involving an oxygen atom and
two carbon atoms.

Asymmetric induction (also enantio-induction) in stereochemistry describes the preferential formation in a

chemical reaction of one enantiomer or diastereoisomer over the other as a result of the influence of a chiral
feature present in the substrate, reagent, catalyst or environment.

Olefin = Alkene

Very basic examples of epoxidation: [Allylic alcohols undergo epoxidation when reacting to t-butyl-hydroperoxide
in presence of catalyst - titanium tetraisopropoxide]

https://www.masterorganicchemistry.com/reaction-guide/sharpless-epoxidation/

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Ideas:

1. Sharpless epoxidation was originally the homogeneous catalysis: it can however be made
heterogeneous by adsorbing the catalyst at the surface – the reaction has already being done. Ref:
http://onlinelibrary.wiley.com/doi/10.1002/1521-3773(20020301)41:5%3C821::AID-
ANIE821%3E3.0.CO;2-A/epdf
2.

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Enantioselctive reactions involving Ni-catalyst:

Notes:

1. Tartaric acid (TA) is the modifier that is used on Ni metal surface for enantioselectivity
2. Very good reference: Asymmetric heterogeneous catalysis: science and engineering, Catalysis Reviews,
47:2, 175-256, DOI: 10.1081/CR-200057461. Link: https://doi.org/10.1081/CR-200057461

Aim:

1. Carry out an enantio-selective reaction in solution (for ease of carrying out the reaction and ease of
characterization) using magnetized Ni surface and observe the enantioselective products.

Enantioselective epoxidation

1. Homogeneous epoxidation of the allylic alcohols

The reaction:
 Catalyst: (+) or (-) diethyl tartrate, Titanium tetraisopropoxide

Notes:

1. The Sharpless epoxidation only works for alkenes adjacent to an alcohol (CH2OH). The oxidant is
t-butyl hydroperoxide abbreviated TBHP. The catalyst is titanium tetraisopropoxide, written. The
additive that imparts chirality is diethyl tartrate (DET).
2. In the above reactions, using molecular sieves can make us use less catalysis. [1987
Sharpless]

Useful link: https://www.masterorganicchemistry.com/reaction-guide/sharpless-epoxidation/

Other examples:

2. Heterogeneous epoxidation of allylic alcohols

 a. Silica supported: Hexagonal mesoporous silica (HMS) is used to bind the catalyst and to make
it heterogeneous.

Ref: Advances in Homogeneous and Heterogeneous Catalytic Asymmetric Epoxidation, Chem. Rev.
2005, 105, 1603-1662.

3. Asymmetric reaction where the surface has a role to play

Reaction
Catalyst
Possibility of doing this reaction on a magnetized surface (Ni)
References

4. Possibility of doing this reaction on a magnetized surface (Ni)

Enantioselective hydrogenation
1. Hydrogenation of beta-ketoesters over chirally modified Ni catalysts (with S-glutamic acid
modifier)

Reaction

Method:
 The Ni{111} sample was cleaned by cycles of ion sputtering (Ar+, 1.5 kV, sample ∼8 μA) and
annealing to 900 K until a sharp (1 × 1) LEED pattern was obtained. The Ni{111} surface was then
exposed to glutamic acid, via sublimation from a solid doser. The temperature of glutamic acid was
monitored via a thermocouple and was maintained at 403 K for all experiments.
 After glutamic acid exposure, the surface was then exposed to 10 L of H2 at a hydrogen partial
pressure of 1 × 10-7 Torr. After pretreatment in hydrogen, the sample was exposed to
methylacetoacetate at 300 K.
  Note 1: Methylacetoacetate (Sigma-Aldrich, 99% purity) was purified by freeze-pump-thaw cycles
before use (verified by mass spectroscopy) and introduced to the Ni{111} sample via background
dosing using a high precision leak valve at 300 K with a dosing pressure of typically ∼1 × 10-10 Torr.
 Note 2: The coverage of modifier on the Ni surface is an important parameter in the optimization
of enantioselectivity.

2. Another reaction (in solution): Hydrogenation of methyl aceto-acetate using Ni-TA:

Asymmetric heterogeneous catalysis: science and engineering, Catalysis Reviews, 47:2, 175-256, DOI:
10.1081/CR-200057461. Link: https://doi.org/10.1081/CR-200057461

In this method, the reaction is carried out either in a glass apparatus or in an autoclave.
Glass apparatus technique: https://www.sciencedirect.com/science/article/pii/002195179290101M