Chelating Bis(thiophosphinic amidate)s as Versatile Supporting Ligands for the Group 3 Metals. An Application to the Synthesis of Highly Active Catalysts for Intramolecular Alkene Hydroamination

Bis(thiophosphinic amidate) complexes (i.e., 1) of representative group 3 and lanthanide metals have been quantiatively prepared in situ from the corresponding thiophosphinic amides and Ln[N(TMS)2]3. These unusual pentacoordinate complexes exhibit very high activity as catalysts for intramolecular alkene hydroamination

Pd-Catalyzed Three-Component Reaction of 3‑(Pinacolatoboryl)ally Acetates, Aldehydes, and Organoboranes: A New Entry to Stereoselective Synthesis of (<i>Z</i>)-<i>anti</i>-Homoallylic Alcohols

The Pd-catalyzed three-component reaction of 3-(pinacolato­boryl)­allyl acetates, aldehydes, and organoboranes is described. The reaction is initiated by the formation of an allylic <i>gem</i>-palladium/boryl intermediate, which then undergoes allylation of aldehydes by allylboronates followed by a coupling reaction of in situ generated (<i>Z</i>)-vinylpalladium acetates with organoboranes to provide the (<i>Z</i>)-<i>anti</i>-homoallylic alcohols with high levels of diastereoselectivity and alkene stereocontrol

Stereoselective Synthesis of Vinylsilanes by a Gold(I)-Catalyzed Acetylenic Sila-Cope Rearrangement

Cationic tri-tert-butylphosphinegold(I) serves as a catalyst in the sila-Cope rearrangement of acetylenic allylsilanes. When phenol is employed as a nucleophile, the reaction allows for the stereoselective synthesis of vinylsilanes. Alternatively, use of methanol as a nucleophile leads to cyclic vinylsilanes, which can be viewed as latent vinylsilanes that are revealed on treatment with a mild Lewis acid. Thus, both of these reagents serve as useful reagents for stereoselective synthesis of trisubstituted olefins through transition-metal-catalyzed cross-coupling reactions

Chelating Bis(thiophosphinic amidate)s as Versatile Supporting Ligands for the Group 3 Metals. An Application to the Synthesis of Highly Active Catalysts for Intramolecular Alkene Hydroamination

Bis(thiophosphinic amidate) complexes (i.e., 1) of representative group 3 and lanthanide metals have been quantiatively prepared in situ from the corresponding thiophosphinic amides and Ln[N(TMS)2]3. These unusual pentacoordinate complexes exhibit very high activity as catalysts for intramolecular alkene hydroamination

Stereoselective Synthesis of Vinylsilanes by a Gold(I)-Catalyzed Acetylenic Sila-Cope Rearrangement

Cationic tri-tert-butylphosphinegold(I) serves as a catalyst in the sila-Cope rearrangement of acetylenic allylsilanes. When phenol is employed as a nucleophile, the reaction allows for the stereoselective synthesis of vinylsilanes. Alternatively, use of methanol as a nucleophile leads to cyclic vinylsilanes, which can be viewed as latent vinylsilanes that are revealed on treatment with a mild Lewis acid. Thus, both of these reagents serve as useful reagents for stereoselective synthesis of trisubstituted olefins through transition-metal-catalyzed cross-coupling reactions

Au(I)-Catalyzed Cycloisomerizations Terminated by sp³ C−H Bond Insertion

Au(I)-Catalyzed Cycloisomerizations Terminated by sp3 C−H Bond Insertio

Trialkylborane-Mediated Multicomponent Reaction for the Diastereoselective Synthesis of <i>Anti</i>-δ,δ-Disubstituted Homoallylic Alcohols

The trialkylborane/O2-mediated reaction of propargyl acetates having a tributylstannyl group at an alkyne terminus with aldehydes in a THF–H2O solvent system gave anti-δ,δ-disubstituted homoallylic alcohols with good to high diastereoselectivity. Intriguingly, two alkyl groups derived from trialkylborane were embedded into the reaction product. The trialkylborane plays a key role not only as a radical initiator but also as a source of alkyl radicals

Pd(0)-Catalyzed Amphiphilic Activation of Bis-allyl Alcohol and Ether

Pd(0)·Et3B catalyzes amphiphilic activation of symmetric allylic diol 1 to promote electrophilic allylation at the α-position of aldehydes and nucleophilic allylation at the aldehyde CO, furnishing 3-methylenecyclopentalols 2 and thus generation of a zwitterionic trimethylenemethane species from the commercially available diol 1

Pronounced Chemo-, Regio-, and Stereoselective [2 + 2] Cycloaddition Reaction of Allenes toward Alkenes and Alkynes

Pronounced Chemo-, Regio-, and Stereoselective [2 + 2] Cycloaddition Reaction of Allenes toward Alkenes and Alkyne

Pd(0)-Catalyzed Amphiphilic Allylation of Aldehydes with Vinyl Epoxide

Under Pd(0)-Et3B catalysis, vinyl epoxide serves as a formal 3-butenyl 2-anion−1-cation equivalent, and the cation reacts with aldehydes at the α-position, and the anion, at the carbonyl carbon, furnishing 2-vinylcyclobutanols in one pot