Table of contents

1. A Review of General Chemistry5h 5m
2. Molecular Representations1h 14m
3. Acids and Bases2h 46m
4. Alkanes and Cycloalkanes4h 17m
5. Chirality3h 39m
6. Thermodynamics and Kinetics1h 22m
7. Substitution Reactions1h 48m
8. Elimination Reactions2h 30m
9. Alkenes and Alkynes2h 9m
10. Addition Reactions3h 19m
11. Radical Reactions1h 58m
12. Alcohols, Ethers, Epoxides and Thiols2h 42m
13. Alcohols and Carbonyl Compounds2h 17m
14. Synthetic Techniques1h 26m
15. Analytical Techniques:IR, NMR, Mass Spect7h 3m
16. Conjugated Systems6h 13m
17. Ultraviolet Spectroscopy51m
18. Aromaticity2h 34m
19. Reactions of Aromatics: EAS and Beyond5h 1m
20. Phenols55m
21. Aldehydes and Ketones: Nucleophilic Addition4h 56m
22. Carboxylic Acid Derivatives: NAS2h 51m
23. The Chemistry of Thioesters, Phophate Ester and Phosphate Anhydrides1h 10m
24. Enolate Chemistry: Reactions at the Alpha-Carbon1h 53m
25. Condensation Chemistry2h 9m
26. Amines1h 43m
27. Heterocycles2h 0m
28. Carbohydrates5h 53m
29. Amino Acids4h 20m
30. Peptides and Proteins2h 42m
31. Catalysis in Organic Reactions1h 30m
32. Lipids 2h 50m
33. The Organic Chemistry of Metabolic Pathways2h 52m
34. Nucleic Acids1h 32m
35. Transition Metals6h 14m
36. Synthetic Polymers1h 49m

16. Conjugated Systems

Photochemical Electrocyclic Reactions

Organic Chemistry

16. Conjugated Systems

Photochemical Electrocyclic Reactions

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3:46 minutes

Problem 20

Textbook Question

Explain why the hydrogen and the methyl substituent are trans to one another after photochemical ring closure of provitamin D₃ to form 7-dehydrocholesterol.

Verified step by step guidance

Understand the context: The photochemical ring closure of provitamin D3 involves a [2+2] cycloaddition reaction, which is a pericyclic reaction. This reaction occurs under UV light and forms a cyclobutane ring. The stereochemistry of the product is determined by the orbital interactions during the reaction.

Recognize the key stereochemical principle: In a [2+2] cycloaddition, the reaction proceeds through the interaction of the π orbitals of the double bonds. The stereochemistry of the substituents in the product is governed by the relative orientation of the reacting π orbitals in the excited state.

Analyze the geometry of the starting material: In provitamin D3, the double bonds involved in the reaction are part of a conjugated triene system. Upon UV irradiation, one of the double bonds is excited to a higher energy state, and the reaction occurs between the excited double bond and the adjacent double bond. The substituents on the reacting carbons are positioned in a way that minimizes steric hindrance and maximizes orbital overlap.

Explain the trans relationship: During the photochemical reaction, the hydrogen and methyl substituents on the reacting carbons are positioned on opposite sides of the forming cyclobutane ring. This trans arrangement is a result of the anti-periplanar alignment of the substituents in the transition state, which minimizes steric clashes and ensures efficient orbital overlap.

Conclude with the product's stereochemistry: The final product, 7-dehydrocholesterol, retains the trans relationship between the hydrogen and methyl substituents because the reaction is stereospecific. The stereochemistry is locked in during the ring closure and reflects the geometry of the transition state.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Photochemical Reactions

Photochemical reactions involve the absorption of light to initiate a chemical change. In the context of organic chemistry, these reactions can lead to the formation of new bonds and rearrangements of molecular structures. Understanding the principles of photochemistry is essential for analyzing how light can influence the spatial arrangement of atoms in a molecule, such as during the ring closure of provitamin D3.

Stereochemistry

Stereochemistry is the study of the spatial arrangement of atoms in molecules and how this affects their chemical behavior. In the case of 7-dehydrocholesterol formation, the trans configuration of hydrogen and methyl substituents is a result of the specific stereochemical pathways taken during the reaction. Recognizing the importance of stereochemistry helps explain why certain substituents adopt specific orientations in the final product.

Ring Closure Mechanisms

Ring closure mechanisms refer to the processes by which linear or open-chain molecules form cyclic structures. In the case of provitamin D3, the photochemical ring closure leads to the formation of a cyclic compound, 7-dehydrocholesterol. The mechanism of this closure, including the orientation of substituents, is crucial for understanding the resulting molecular geometry and the implications for biological activity.

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