The Stille Reaction

MECHANISTIC CONSIDERATIONS, REGIOCHEMISTRY AND STEREOCHEMISTRY.

SCOPE AND LIMITATIONS: THE ELECTROPHILE.

Alkenyl Halides.

Aryl and Heterocyclic Halides.

Acyl Chlorides.

Allylic, Benzylic, and Propargylic Electrophiles.

Alkenyl Sulfonates and Other Electrophiles.

Aryland Heterocyclic Sulfonates and Other Derivatives.

Miscellaneous Electrophiles.

SCOPE AND LIMITATIONS: THE STANNANE.

Alkylstannanes.

Alkenylstannes.

Aryl and Heterocyclic Stannanes.

Alkynylstannanes.

Allylstannanes.

Other Stannanes.

CARBONYLATIVE COUPLINGS.

Alkenyl Halides.

Aryl and Heterocyclic Halides.

Allylic and Benzylic Halides.

Alkenyl Sulfonates.

Aryl and Heterocyclic Sulfonates.

Miscellaneous Substrates.

COMPLEX SYNTHETIC SEQUENCES INVOLVING TIN-TO-PALLADIUM (II) METATHESIS STEPS.

SIDE REACTIONS.

Homocoupling Reactions.

Transfer of "Nontransferable" Ligands.

Destannylation.

Cine Substitution.

Phosphorus-to-Palladium Aryl Migration.

Electrophile Reduction.

Product Isomerization.

Miscellaneous Side Reactions.

COMPARISON WITH OTHER METHODS.

EXPERIMENTAL CONDITIONS.

The Stannane: Preparation and Handling.

Alkenyl and Aryl Triflates.

Choice of Nontransferable Ligands.

Choice of Catalyst and Ligands.

Choice of Solvent.

Additives.

Workup: Removal of Tin Halides.

EXPERIMENTAL PROCEDURES.

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].

TUBULAR SURVEY.

Tables.

References.