advanced organic reactions

1. Buchwald-Hartwig Coupling
&
Click reaction
U-5 New synthetic Organic Reactions
B.SATEESH KUMAR
L.IN CHEMISTRY,GDCM SKLM
III BSc Chemistry
Semester-VI
Paper- VIII C-2
Part-8

2. Outlines
• U-5 Total syllabus
• Short notes on coupling reactions
• About the Buchwald - hartwig Coupling Reaction
Statement with equation
Mechanism
• About Click Reaction
Statement with equation
Mechanism
• Conclusions
B SATEESH KUMAR , L IN CHEMISTRY , GDC M SKLM

3. Unit-5
[New synthetic reactions]
1. Baylis-Hillmann reaction
2. Grubbs catalysts
3. Grubbs RCM olefin metathesis reaction
4. Mukayama aldol reaction
5. Mcmurry reaction
6. Mitsnobu reaction
7. Julia-lythgoe olefination
8. Peterson olefination
9. Heck reaction
10. Suzuki coupling
11. Stille coupling
12. Sonogishira coupling
13. Buchwald - hartwig coupling
14. Click reaction
15. Ugi reaction
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4. Buchwald - Hartwig Coupling
Reaction
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Start
with

5. About the reaction
•It is a one of the amination reaction in organic chemistry
•In this reaction a new C-N bond formation reaction
•This Buchwald–Hartwig amination reaction is a palladium-catalyzed
cross coupling reaction.
•Here new C-N bond formed between of amines with aryl halides
•In this coupling reaction requirement of Base is important.
B SATEESH KUMAR , L IN CHEMISTRY , GDC M SKLM

6. Statement
B SATEESH KUMAR , L IN CHEMISTRY , GDC M SKLM
“Coupling of aryl halide and a primary or secondary amine in the
presence of base and palladium(0) catalyst to form aryl amine.
This coupling reaction is known as a Buchwald - hartwig Coupling
reaction”.

7. Aryl halide
Reaction
B SATEESH KUMAR , L IN CHEMISTRY , GDC M SKLM
AMINE Aryl amines

8. It is a Catalytic cycle mechanism I
Consists of 3 main steps
namely
1. Oxidative Addition
2. Substitution of amine
3. Reductive elimination
Mechanism
B SATEESH KUMAR , L IN CHEMISTRY , GDC M SKLM

9. TOTAL MECHANISM
OXIDATIVE ADDITION
SUBSTITUTION
REDUCTIVE
ELIMINATION
1
2
3
B SATEESH KUMAR , L IN CHEMISTRY , GDC M SKLM

10. Click reaction
2
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11. 1. The classic click reaction is the copper-catalyzed reaction of an azide
with an alkyne to form a 5-membered heteroatom ring this reaction is
known as a Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC).
2. The first triazole synthesis, from diethyl acetylenedicarboxylate and
phenyl azide, was reported by Arthur Michael in 1893.
CLICK REACTION
B SATEESH KUMAR , L IN CHEMISTRY , GDC M SKLM

12. The 1,3-dipolar cycloaddition is a chemical reaction between
a 1,3-dipole and a dipolarophile to form a five-membered ring.
1,3-dipolar cycloaddition
B SATEESH KUMAR , L IN CHEMISTRY , GDC M SKLM

13. Reaction
1,3 dipolar addition Organo azide with alkyne in the presence o heat to
form 1,2,3 triazole
1,2,3 triazole

14. Clear cut reaction

15. 1. Have a simple reaction conditions
2. Use readily available starting materials and reagents
3. Use no solvent or use a solvent that is benign or easily
removed (preferably water)
4. Provide simple product isolation by non-
chromatographic methods (crystallisation or distillation)
5. Have high atom economy.
The process would
preferably

16. Thank You
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