Joseph A. Miller

Palladium-catalyzed acylation of organozincs and other organometallics as a convenient route to ketones☆

Abstract The reaction of organozincs with acyl chlorides catalyzed by palladium-phosphine complexes, e.g., Pd(PPh 3 ) 4 , provides a highly general and convenient route to ketones.

Preparation of unsymmetrical biaryls via Ni- or Pd-catalyzed coupling of aryl chlorides with arylzincs

Abstract Unsymmetrical biaryls may be prepared in an efficient manner using aryl chlorides as substrates in Negishi-type cross-coupling reactions with arylzinc reagents via either Ni- or Pd-catalysis. Since a wide range of functional groups (e.g., nitrile, carbonyl, ester) tolerate arylzinc compounds, this methodology allows for the direct synthesis of biaryls from aryl chlorides possessing these moieties.

Synthesis of functionally substituted unsymmetrical biaryls via a novel double metal catalyzed coupling reaction

Abstract Unsymmetrical biaryls containing “reactive” functional groups (e.g., nitrile or ester groups) can be synthesized in an efficient manner by the direct Ni- or Pd-catalyzed coupling of aryl halides (X = Cl, Br, I) with aryl Grignard (or -lithium) reagents, provided that a catalytic amount of a Zn or Cd salt is also present.

Reaction of alkenes and dienes with t-butylmagnesium halides and zirconocene dihalides. A convenient procedure for hydrozirconation and a novel t-butylzirconation of conjugated alkenes

Abstract The reaction of nonconjugated monosubstituted alkenes with t-BuMgCl and Cl2ZrCp2 at room temperature produces the corresponding monoalkylzirconium derivatives in high yields, while conjugated alkenes undergo either a novel t-butylzirconation or hydrozirconation depending on the reaction conditions.

Zirconium-catalyzed allylalumination and benzylalumination of alkynes

Abstract Allylalanes or benzylalanes react with either terminal or internal alkynes in the presence of a catalytic amount of Cl 2 ZrCp 2 to produce in high yields cis-carboalumination products.

The formation of medium-sized rings by the intramolecular cyclization of arylnitrenium ions

The synthesis of an aminodibenzo[a,c]octadiene and an aminodibenzo[a,c]octatriene, guided by molecular mechanics calculations, was effected by the intramolecular cyclization of the corresponding open chain nitrenium ions. Also reported is the predicted failure to synthesize another aminodibenzo[a,c]octadiene using this method.

Reverse saturable absorption and anti-Stokes fluorescence in mesoionic compounds pumped at 532 nm

Reverse saturable absorption and fluorescence in liquid solutions of mesoionic compounds are reported. Intensity-dependent transmittance and anti-Stokes fluorescence were observed when the samples were excited with radiation at 532 nm. The results are attributed to excited-state absorption, and the process is understood based on quantum-chemistry calculations that allow the energy levels that correspond to the relevant transitions to be located. A phenomenological description of the nonlinear beam propagation inside the samples is presented, and the nonlinear absorption coefficient as well as the saturation intensity is determined.