Organic Superbase-Catalyzed Aldol Type Reactions

During the last two decades, chemists have witnessed the explosive growth of organocatalysis, which provides a robust methodology for the preparation of numerous valuable compounds. The importance of organocatalysis in organic chemistry had been highlighted through the Nobel Prize in Chemistry 2021 was given to Prof. David W.C. MacMillan and Prof. Benjamin List for outstanding contributions to “the development of asymmetric organocatalysis”. Compared to the classical transition-metal catalysis and biocatalysis, organocatalysis has a number of unique properties, such as transition-metal-free, very good structural amenability, novel modes of activations, easy availability of a broad variety of naturally occurring small organic catalysts, including natural sources of chiral amino acids, Cinchona alkaloids, carbenes and others. Today, organocatalysis has been a powerful technology for organic synthesis. In addition to the applications in organic synthesis and catalysis, organocatalysis has also been used in the production of enantiomers, in fine chemistry, pharma, crop-protection, and fragrance chemistry. As one important type of organic catalyst, N-heterocyclic carbenes (NHCs) have broad applications in organic synthesis. Inspired by the natural coenzyme thiamine (vitamin B1) catalysis, chemists developed various NHCs and used them to catalyze a broad variety of transformations, including benzoin reaction, Stetter reaction, homoenolate transformations, redox reactions, cycloadditions, photoreactions and other reactions. On the other hand, aldol condensation reaction is one of the most important reactions for the construction of carbon-carbon bonds. Based on the unique Lewis basicity of NHCs, we and other groups realized efficient activation of different silylated nucleophiles and developed a variety of aldol-type reactions of carbonyl compounds. As a result, different functionalized alcohols and their derivatives were prepared through NHC catalysis.

This book can be used as a reference for scholars, graduate students, and researchers in the field of organic chemistry, fine chemistry and drug synthesis.

Sample Chapter(s)
Preface (75 KB)

Components of the Book:

Preface

Brief Introduction of the Authors

Chapter 1. Organic superbase catalyzed vinylogous aldol reaction of carbonyl compounds

1. N-Heterocyclic carbene catalyzed vinylogous aldol reaction of 2-(trimethylsilyloxy)furan and aldehydes
2. N-Heterocyclic carbene-catalysed vinylogous Mukaiyama aldol reaction of α-ketoesters and α-trifluoromethyl ketones
3. Diastereoselective synthesis of γ-butenolides catalyzed by potassium tert-butoxide
4. N-Heterocyclic carbene-catalyzed fluorinated silyl-Reformatsky reaction of aldehydes and difluoro (trimethylsilyl) acetate
5. N-Heterocyclic carbene mediated Reformatsky reaction of aldehydes with α-trimethylsilylcarbonyl compounds

Chapter 2. Organic superbase catalyzed phospho-aldol reaction of carbonyl compounds

6. N-Heterocyclic carbenes catalyzed phospho-aldol reaction of aldehydes
7. N-Heterocyclic carbene catalyzed hydrophosphonylation of aldehydes
8. Nucleophilic carbene-mediated hydrophosphonylation of aldimines
9. NHCs catalyzed hydrophosphonylation of 𝛼-ketoesters and 𝛼-trifluoromethyl ketones
10. Hydrophosphonylation of aldimines under catalysts-free conditions

Chapter 3. Organic superbase catalyzed other aldol type reactions

11. N-Heterocyclic carbene catalyzed cyanation reaction of carbonyl compounds with ethyl cyanoformate and acetyl cyanide
12. N-Heterocyclic carbenes mediated cyano-phosphorylation of ketones
13. Organocatalytic direct difluoromethylation of aldehydes and ketones with TMSCF2
14. N-Heterocyclic carbene-catalysed pentafluorophenylation of aldehydes
15. N-Heterocyclic carbene catalyzed additions of 3-trimethylsilyl propiolate to aldehydes
16. N-Heterocyclic carbene-catalysed Peterson olefination reaction
17. N-Heterocyclic carbene-catalyzed switchable reaction of 9-(trimethylsilyl)fluorene and aldehydes: chemoselective synthesis of dibenzofulvenes and fluorenyl alcohols
18. Organocatalytic aminocarbonylation of α,β-unsaturated ketones with N, N-dimethyl carbamoylsilane
19. Asymmetric desymmetrization of 1,3-diketones via intramolecular benzoin reaction

Conclusions

Readership: Students, academics, teachers and other people attending or interested in the field of organic chemistry, fine chemistry and drug synthesis

1		Preface Guangfen Du, Fang Zhang PDF (75 KB)

3		Brief Introduction of the Authors Guangfen Du, Fang Zhang PDF (160 KB)

1		Chapter 1. Organic superbase catalyzed vinylogous aldol reaction of carbonyl compounds Guangfen Du, Fang Zhang PDF (1023 KB)

51		Chapter 2. Organic superbase catalyzed phospho-aldol reaction of carbonyl compounds Guangfen Du, Fang Zhang PDF (925 KB)

101		Chapter 3. Organic superbase catalyzed other aldol type reactions Guangfen Du, Fang Zhang PDF (1836 KB)

203		Conclusions Guangfen Du, Fang Zhang PDF (97 KB)

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Guangfen Du
She received her B.S. in chemical engineering and technology from Qufu Normal University in 2002 and her M.Sc. in material physics and chemistry from the University of Science and Technology of China in 2005. Then, she joined Linyi University as a lecture. In 2008 she moved to Shihezi University and in 2012, she began her Ph.D. study under supervision of Prof. Bin Dai at Tianjin University. In 2016, She got a Ph.D. degree from Tianjin University in applied chemistry.

Fang Zhang
He was born in Ji Ning, P. R. of China in 1998. He obtained his B.S. in applied chemistry from Shihezi University in 2020. He is currently a Ph.D. student in the research group of Professor Guangfen Du at Shihezi University. His research interests focus on the discovery and development of new methods for organic synthesis.

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