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Reactive Intermediate Chemistry

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CHAPTER 7

Singlet Carbenes

MAITLAND JONES, Jr.

Department of Chemistry, Princeton University, Princeton, NJ

ROBERT A. MOSS

Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, NJ

1.

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

274

 

1.1. Prototypal Reactions: Addition and Insertion Reactions . . . . . . . . . . . . . .

274

 

1.2. Structure and Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

274

2.

More Detailed Treatments of Structure and Prototypal Reactions . . . . . . . . . . .

279

 

2.1. Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

279

 

2.1.1. Philicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

279

 

2.1.2. Rates and Activation Parameters . . . . . . . . . . . . . . . . . . . . . . . . .

285

 

2.1.3. Symmetry of the Transition State . . . . . . . . . . . . . . . . . . . . . . . .

289

 

2.1.4. Stepwise versus Concerted Addition . . . . . . . . . . . . . . . . . . . . . .

291

 

2.2. Carbon–Hydrogen Insertion Reactions . . . . . . . . . . . . . . . . . . . . . . . . . .

298

 

2.2.1. Intermolecular Insertions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

298

 

2.2.2. Intramolecular Insertions: Rearrangements . . . . . . . . . . . . . . . . . .

302

 

2.3. Singlet–Triplet Equilibration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

307

 

2.4. Carbene Mimics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

308

 

2.4.1. Solvent Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

313

 

2.5. The Phenylcarbene Rearrangement: The Chemistry of an

 

 

Incarcerated Carbene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

314

 

2.6. Fragmentation of Alkoxycarbenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

317

3.

Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

320

Suggested Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

321

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

321

Reactive Intermediate Chemistry, edited by Robert A. Moss, Matthew S. Platz, and Maitland Jones, Jr. ISBN 0-471-23324-2 Copyright # 2004 John Wiley & Sons, Inc.

273

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