Steric and stereoelectronic effects in organic chemistry / Veejendra K. Yadav.

Format:

Book

Author/Creator:

Yadav, V. K., author.

Language:

English

Subjects (All):

Stereochemistry--Programmed instruction.

Stereochemistry.

Chemistry, Organic.

Physical Description:

1 online resource (271 pages)

Edition:

2nd ed.

Place of Publication:

Cham, Switzerland : Springer, [2021]

Summary:

In this second edition, the author has thoroughly updated each chapter and expanded the content with addition of three new chapters. This book comments on several key aspects of stereochemical control of organic reactions in measured detail to allow the reader easily grasp these concepts. In addition, emphasis is given to key information and important aspects of steric and stereoelectronic effects and their control on conformational profile and reactivity features. This book is not only an indispensable resource for advanced undergraduate and graduate students studying the stereochemical aspects of organic reactions, but also a good reference book for all organic chemists in both industry and academia.

Contents:

Intro

Preface to the Second Edition

Summary of Second Revised Edition

Contents

About the Author

1 Steric and Stereoelectronic Control of Molecular Structures and Organic Reactions

1 Influence of Steric Effects on Structures

2 Influence of Stereoelectronic Effects on Reactions

3 Evaluation of the Numerical Value of Anomeric Effect

4 Influence of Anomeric Effect on Conformational Preferences

5 Influence of Anomeric Effect on Conformational Reactivity

6 Conformations of Mono and Dithioacetals

7 Conformations of Mono and Diazaacetals

8 Antiperiplanar Effects Arising from C-Si, C-Ge, C-Sn, and C-Hg Bonds

References

2 Reactions on Saturated and Unsaturated Carbons

1 Inter- and Intramolecular Reactions on Saturated Carbons

2 Intermolecular Reactions of Epoxides

3 Intramolecular Reactions of Epoxides

4 Baldwin Rules for Ring Closure on Saturated and Unsaturated Carbons

5 SN2' Reaction (Reaction on Unsaturated Carbon)

6 SN2 Reaction of Cyclopropane Activated by Two Geminal Carbonyl Groups

7 Reactions Involving Consecutive Intramolecular SN2 Reactions Leading to Rearrangement

8 Dual Activation for Skeletal Rearrangement

9 Solvolysis with Neighboring Group Participation

10 Rearrangement Originating from Oxirane Under Lewis Acid Condition

11 Rearrangement via Classical Versus Nonclassical Carbocations

12 Tandem Skeletal Changes and Polyene Cyclization

13 Application of 5-Exo-Trig Cyclization Rule

14 Stereocontrol in Multi-cyclization Reactions

15 Reaction on sp Carbons

16 Stereoelectronic Control in Beckmann Rearrangement

17 Stereoelectronic Control in Curtius Rearrangement

3 Diastereoselectivity in Organic Reactions

1 Introduction

2 Cram's Model for Asymmetric Synthesis

3 Anh-Felkin Modification of Cram's Model for Asymmetric Synthesis.

4 Cieplak's Model for Diastereoselectivity

5 Houk's Transition State and Electrostatic Models for Diastereoselectivity

6 Cation Coordination Model (σ → π* Model) for Diastereoselectivity

5-Aza-2-Adamantanone, 18

N-Methyl-5-Aza-2-Adamantanone, 19

5-Aza-2-Adamantanone N-Oxide, 20

5-Bora-2-Adamantanone, 21

2,3-Endo,Endo-Dimethylnorbornan-7-One and the Corresponding Diethyl Analog

4-Oxatricyclo[5.2.1.02,6]Decan-10-One, 9, and 4-Oxatricyclo[5.2.1.02,6]Dec-8-En-10-One, 10

Trans-2-Heterobicyclo[4.4.0]Decan-5-Ones

3-Halocyclohexanones

4 A(1,2) and A(1,3) Strains

2 A(1,2) Strain

3 Stereocontrol in Reactions on Account of A(1,2) Strain

4 A(1,3) Strain

5 Stereocontrol in Reactions on Account of A(1,3) Strain

6 A(1,3) Strain in Amides and Its Consequences on Diastereoselectivity

5 The Conservation of Orbital Symmetry Rules (Woodward-Hoffmann Rules)

2 Orbitals and Symmetry Considerations

3 π2 + π2 Reaction

4 Electrocyclic Ring Closure and Ring Opening Reactions

1,3-Butadiene → Cyclobutene

1,3,5-Hexatriene → 1,3-Cyclohexadiene

5 Diels-Alder Cycloaddition Reaction (π4 + π2 Reaction)

6 The Overlap Component of the Stereoelectronic Effect vis-à-vis the Conservation of Orbital Symmetry Rules

2 Steric Effects in the Thermal Fragmentation of cis-3,6-Dimethyl-3,6-Dihydropyridazine

3 Orbital Overlap Effects in the Thermal Fragmentation of Cyclopropanated and Cyclobuanated cis-3,6-Dimethyl-3,6-Dihydropyridazine

4 Orbital Overlap Effects in [1,5] Sigmatropic Shifts

5 Difficulties Experienced with [1,5]-Sigmatropic in the Cyclobutanated Species

7 Torquoselectivity of Conrotatory Ring Opening in 3-Substituted Cyclobutenes

1 Activation Barrier Approach to Torquoselectivity.

2 TS-NBO Approach to Torquoselectivity

3 Restricted Conformational Effects on Torquoselectivity

4 Global Conformational Effects on Torquoselectivity

8 Hammett Substituent Constants

1 Hammett Substituent Constants for Benzoic Acids (σm and σp)

2 Hammett Substituent Constants for Phenylacetic and 3-Arylpropionic Acids

3 Hammett Substituent Constants and Free Energy Assessment

4 Hammett Substituent Constants and Reaction Pathway Relationship

5 Hammett Substituent Constants σ+ and σ−

6 Hammett Substituent Constants and Ester Hydrolysis Mechanism

9 Relative Aromaticity of Pyrrole, Furan, Thiophene and Selenophene, and Their Diels-Alder Stereoselectivity

2 Heteroatom Lone Pair Interaction with Ring π Bonds in the Ground State

3 DA Reactions of Pyrrole, Furan, Thiophene, and Selenophene with MA

4 DA Reactions of Cyclopentadiene, Silole, and Germole with MA

5 DA Reactions of Cyclopentadiene, Silole, and Germole with Acetylene-1,2-Bisnitrile and Acetylene

6 DA Reactions of 1,3-Cyclohexadiene and 1,3-Cycloheptadiene with MA

7 DA Reactions of 1,3-Cyclohexadiene and 1,3-Cycloheptadiene with Acetylene-1,2-Bisnitrile and Acetylene

8 DA Reactions of 1,3-Cyclohexadiene and 1,3-Cyclooctadiene-6-Yne with Acetylene-1,2-Bisnitrile and Acetylene

9 Evaluation of Allylic Interaction in DA Reactions of Acyclic Dienes

10 DA Reactions of 6-Oxa-, 6-Aza-, 6-Thia-, and 6-Selena-1,3-Cycloheptadienes with MA

11 DA Reactions of 2,3-Cyclopropano-, 2,3-Cyclobutano-, and 2,3-Cyclopentano-6-Oxa-1,3-Cycloheptadienes with MA

12 DA Reactions of Benzene, Pyridine, and 1,4-Diazine with Acetylene-1,2-Bisnitrile and Acetylene

13 DA Reactions of Naphthalene, 1-Azanaphthalene, and 1,4-Diazanaphthalene with Cyclopropene.

14 DA Reactions of Anthracene, 9-Azaanthracene, and 9,10-Diazaanthracene with Cyclopropene

15 DA Reactions of Benzene, Naphthalene, and Anthracene with Acetylene-1,2-Bisnitrile

16 Deformation Energy Considerations in DA Reactions of Five-Membered Heterocycles with Acetylene-1,2-Bisnitrile

17 DA Reactions of Thiophene 1,1-Dioxide with MA

18 Reaction Profile and Solvent Effects on Diastereoselectivity of DA Reactions of Five-Membered Heterocycles with MA

10 Miscellaneous

1 Spiroconjugation

2 Periselectivity

3 Ambident Nucleophiles

4 Ambident Electrophiles

α,β-Unsaturated Carbonyl Compounds

Aromatic Electrophiles

Unsymmetrical Anhydrides

Arynes

5 α-Effect

6 Carbenes

7 Hammond Postulate

8 Curtin-Hammett Principle

9 Diastereotopic, Homotopic, and Enantiotopic Substituents

10 Captodative Effect

Questions.

Notes:

Description based on print version record.

ISBN:

3-030-75622-X

OCLC:

1259627714