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cascade reaction

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94 views15 pages

Cascade Reactions Presentation

cascade reaction

Uploaded by

swarupcool390
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Cascade Reactions

Swarup Behera
C0211554

10/20/2024 1
Presentation Outline

 Definition of Cascade Reaction


 Importance of Cascade Reaction
 Examples of Cascade Reaction
 Classification of Cascade Reaction

10/20/2024 2
Definition

 Cascade reaction is a chemical process that comprises at least two


consecutive reactions such that each subsequent reaction occurs only
in virtue of the chemical functionality formed in the previous step.

 Simply, It is a process involving two or more bond forming


transformations (usually C–C bonds), which take place under the same
reaction conditions without adding additional reagents and catalysts
and in which the subsequent reactions result as a consequence of the
functionality formed in the previous step.

10/20/2024 3
Cascade Reaction

 In cascade reaction,

o Isolation of intermediate is not possible

o Reaction condition does not change among consecutive steps of cascade

o No reagents are added after the initial step

 A cascade reaction is also called tandem reaction or domino reaction.

10/20/2024 4
Cascade Reaction

 A cascade reaction must satisfy three criteria:

1. Multiple transformations are achieved in a single pot.

2. In this single pot, a single set of reaction conditions is maintained

3. Each transformation is dependent on the preceding transformation.

10/20/2024 5
Importance of cascade reaction

Usual procedure for synthesis of organic compounds

Stepwise formation of individual bonds in the target molecule

More efficient approach

Formation of several bonds in one sequence without isolating intermediates

No need to change reaction conditions or add reagents

Result: Ecologically and economically favorable production 10/20/2024 6


Classification of cascade reaction

Cascade Reaction
(Based on the mechanism of the first step )

Nucleophilic Transition
or Radical Pericyclic metal-
Electrophilic catalyzed

10/20/2024 7
Nucleophilic/electrophilic cascades

• Nucleophilic/electrophilic cascades are defined as the cascade sequences


in which the key step constitutes a nucleophilic or electrophilic attack.

The chiral epoxy-alcohol 1 was first treated with


dichloroacetonitrile in the presence of NaH. The
resulting intermediate 2 then underwent a
BF3·Et2O-mediated cascade reaction.
Intramolecular opening of the epoxide ring
yielded intermediate 3, which, after an in
situ hydrolysis facilitated by excess BF3·Et2O,
afforded (–)-chloramphenicol (4) in 71% overall
yield.

10/20/2024 8
Organocatalytic cascades

• A subcategory of nucleophilic/electrophilic sequences is constituted by


organocatalytic cascades, in which the key nucleophilic attack is driven by
organocatalysis.

Treatment of the enone starting


material 13 with
organocatalyst 14 yielded
intermediate 15 via conjugate addition.
Subsequent cyclization by the
intramolecular Michael addition of the
enolate into the triple bond of the system
gave species 16, which afforded
intermediate 17 after proton transfer and
tautomerization. The cascade was
completed by elimination of the
organocatalyst and a spontaneous 6π-
electrocyclic ring closure of the
resultant cis-dienone 18 to (+)-
harziphilone (19) in 70% overall yield. 10/20/2024 9
Radical cascades

• Radical cascades are those in which the key step constitutes a radical reaction.
• The high reactivity of free radical species renders radical-based synthetic approaches
decidedly suitable for cascade reactions.

Aryl bromide 33 was converted to the


corresponding radical species 34 by treatment with
tri-n-butyltin hydride. A 5-exo-trig cyclization then
occurred to give intermediate 35 stereoselectively
in virtue of the stereochemistry of the ether
linkage. In the next step of the cascade, the
geometric constraints of 35 forbid the kinetically
favored 5-exo-trig cyclization pathway; instead
secondary benzylic radical species 36 was
obtained via a geometrically-allowed 6-endo-trig
cyclization. Subsequent elimination of the phenyl
sulfinyl radical afforded product 37 in 30% overall
yield, which was further elaborated to (–)-morphine
(38).

10/20/2024 10
Pericyclic cascades

• Pericyclic reactions include cycloadditions, electrocyclic reactions and


sigmatropic rearrangements.

• Although some of the abovementioned instances of


nucleophilic/electrophilic and radical cascades involved pericyclic
processes, this section contains only cascade sequences that are solely
composed of pericyclic reactions or in which such a reaction arguably
constitutes the key step.

10/20/2024 11
Pericyclic cascades

the highly unsaturated system 39 was first


hydrogenated to the conjugated tetraene
species 40, which upon heating underwent an 8π-
conrotatory electrocyclic ring closure, yielding
cyclic intermediate 41. A second spontaneous
electrocyclization, this time a 6π-disrotatory ring
closure, converted 41 to the bicyclic species 42,
the geometry and stereochemistry of which
favored a subsequent intramolecular Diels-Alder
reaction. The methyl ester of endiandric acid B (43)
was thus obtained in 23% overall yield.

10/20/2024 12
Transition-metal-catalyzed cascades

• Transition-metal-catalyzed cascade sequences combine the novelty and


power of organometallic chemistry with the synthetic utility and economy
of cascade reactions, providing an even more ecologically and
economically desirable approach to organic synthesis.

Rhodium catalysis was used to convert acyclic monoterpenes of the type 59 to 4H-chromen
products in a hydroformylation cascade (Scheme 12).First, selective rhodium-catalyzed
hydroformylation of the less sterically hindered olefin bond in 59 yielded unsaturated
aldehyde 60, which under the same conditions was then converted to intermediate 61 via a
carbonyl-ene reaction. A second rhodium-catalyzed hydroformylation to species 62 was followed
by condensation to form 4H-chromen products of the type 63 in 40% overall yield.
10/20/2024 13
References

 Cascade Reactions in Organic Chemistry - Baran Lab

(https://baranlab.org/wp-content/uploads/2018/02/Cascade_reactions_Reisberg2018.pdf
)

 Wikipedia

(https://en.wikipedia.org/wiki/Cascade_reaction)

10/20/2024 14
THANK YOU

10/20/2024 15

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