Compatible with virtually all functional groups without protection and capable of forming carbon–carbon bonds under neutral conditions–often with complete stereospecificity–the Stille reaction is an indispensable component of the synthetic organic chemist′s toolkit. In the years since Stille′s pioneering work, chemists have developed a vast number of applications for this incredibly versatile metal–catalyzed cross–coupling reaction. This paperback edition of the 50th volume in the definitive Organic Reactions series describes many of those uses.
Drawing upon their considerable experience as professional synthetic organic chemists who have worked extensively with the Stille reaction, the authors approach their subject from the preparative viewpoint, paying particular attention throughout to limitations, interfering influences, effects of structure, and the selection of experimental techniques. Focusing primarily on the single reaction of the Stille reaction, they provide comprehensive coverage of:
∗ Experimental conditions and selecting optimal experimental parameters
∗ Traditional and recently developed experimental procedures
∗ Side reactions and techniques for avoiding them
∗ Documented reactions–33 tables list 570 reactions, complete withconditions, yields, structures of major products, and common failures
∗ Easy–to–follow recipes for casual users of the Stille reaction
The Stille Reaction is an indispensable working resource for all synthetic organic chemists, especially medicinal chemists. It is also an excellent graduate–level text for students of organic and medicinal chemistry.
SCOPE AND LIMITATIONS: THE ELECTROPHILE.
Aryl and Heterocyclic Halides.
Allylic, Benzylic, and Propargylic Electrophiles.
Alkenyl Sulfonates and Other Electrophiles.
Aryland Heterocyclic Sulfonates and Other Derivatives.
SCOPE AND LIMITATIONS: THE STANNANE.
Aryl and Heterocyclic Stannanes.
Aryl and Heterocyclic Halides.
Allylic and Benzylic Halides.
Aryl and Heterocyclic Sulfonates.
COMPLEX SYNTHETIC SEQUENCES INVOLVING TIN–TO–PALLADIUM (II) METATHESIS STEPS.
Transfer of "Nontransferable" Ligands.
Phosphorus–to–Palladium Aryl Migration.
Miscellaneous Side Reactions.
COMPARISON WITH OTHER METHODS.
The Stannane: Preparation and Handling.
Alkenyl and Aryl Triflates.
Choice of Nontransferable Ligands.
Choice of Catalyst and Ligands.
Choice of Solvent.
Workup: Removal of Tin Halides.
Trimethyl([3–(Cyclohexen–1–yl)–2–Propynyl)silane [Cross–Coupling of a Vinyl Halide with an Alkynylstannane Using Pd(PPh—3)—2Cl—2].
4–tert Butyl–1–Vinylcyclohexene [Cross–Coupling of a Vinyl Triflate with a Vinylstannane Using Pd(PPh—3)—4 and LiCl].
1–(4–Methoxyphenyl)–4–tert–Butylcyclohexene [Cross–Coupling of a Vinyl Triflate with an Arylstannane Using Pd—2(dba)—3 and AsPh—3].
3–Methyl–2–(4–Tolyl)–2–Cyclopentenone [Cross–Coupling of an Unreactive Alkenyl Halide under "Modified" Conditions Using Pd(PhCN)—2Cl—2 AsPh—3, and Cul as Cocatalyst].
1–(4–Nitrophenyl)–2–Propenone (Cross–Coupling of an Acid Chloride with an Arylstannane).
4–Allylacetophenone [Cross–Coupling of an Aryl Triflate under Mild Conditions using Tri(2–Furyl)Phosphine as Ligand.
8–(Trimethylstannyl)Quinoline (Preparation of an Arylstannane by Cross–Coupling and Aryl Triflate with Hexamethyldistannane).
4–(tert–Butyl–1–Vinylcyclohexen–1–Yl)–2–Propenone [Carbonylative Cross–Coupling of an Alkenyl Triflate with an Alkenylstannane using Pd(PPh—3)—4 and LiCl].
(E)–1–(4–Methoxphenyl)–3–Phenyl–2–Propenone [Carbonylative Cross–Coupling of an Aryl Triflate with an Alkenylstannane using Pd(dppf)Cl—2 and LiCl].
VENKAT KRISHNAMURTHY, PhD, is a research chemist with Occidental Chemical Corporation.
WILLIAM J. SCOTT is a research chemist with the Bayer Corporation Institute of Chemistry, Department of Medicinal Chemistry.