Synthesis of 2,3-Diarylisoindolin-1-one by Copper-Catalyzed Cascade Annulation of 2-Formylbenzonitriles, Arenes, and Diaryliodonium Salts.

A three-component cascade cyclization was developed to synthesize 2,3-diarylisoindolin-1-one by using 2-formylbenzonitrile, arenes, and diaryliodonium salts. The process underwent copper-catalyzed tandem C-N/C-C bond formation, producing isoindolin-1-one derivatives in good to excellent yields.

Reactivity of ruthenium vinylidene complexes containing indenyl/dppe ligands and unsaturated bonds at Cδ with trimethylsilyl azide.

This study presents a new reaction of cationic vinylidene complexes with Me3SiN3 (TMSN3), which yields N-coordinated nitrile complexes 3. Treatment of a ruthenium acetylide precursor containing indenyl and dppe ligands with a series of organic halides produced the corresponding vinylidene complexes 2 in good yield. Further reaction of 2 with TMSN3 at room temperature produced N-coordinated ruthenium nitrile complexes 3. Unlike the reaction of cyclopropenylruthenium complexes with TMSN3, which yielded different products depending on the substituent at Cγ, the vinylidene complexes containing unsaturated bonds at Cd yielded similar N-coordinated nitrile complexes. This transformation did not seemingly occur in the reaction of ruthenium vinylidene complexes containing Cp and PPh3 ligands with TMSN3. Deprotonation of these vinylidene complexes yielded cyclopropenyl or thermodynamic furylruthenium complexes, depending on the substitute at Cγ. Subsequent reactions of the cyclopropenyl or furylruthenium complexes with TMSN3 afforded different products.

[1,4-Bis(diphenyl-phosphan-yl)butane-κP,P']chlorido(η-inden-yl)ruthenium(II).

Facile ligand substitution is observed when the ruthenium chloride complex [Ru(η(5)-C(9)H(7))Cl(PPh(3))(2)] is treated with 1,4-bis-(diphenyl-phosphan-yl)butane in refluxing toluene yielding the title compound, [Ru(C(9)H(7))Cl(C(28)H(28)P(2))]. The Ru(II) atom has a typical piano-stool coordination, defined by the indenyl ligand, one Cl atom and two phosphanyl P atoms. The Ru-P bond lengths are 2.2502 (9) and 2.2968 (8) Å.

Azido-[1,2-bis-(diphenyl-phosphan-yl)ethane-κP,P'](η-inden-yl)ruthenium(II).

Facile ligand substitution is observed when the ruthenium chloride complex [Ru(η(5)-C(9)H(7))Cl(dppe)] (dppe is diphenylphosphanyl ethane) is treated with NaN(3) in refluxing ethanol, yielding the title compound, [Ru(η(5)-C(9)H(7))(N(3))(dppe)] or [Ru(C(9)H(7))(N(3))(C(26)H(24)P(2))]. The Ru(II) atom has a typical piano-stool coordination. The Ru-P bond lengths are 2.284 (2) and 2.235 (2) Å. NMR and MS analyses are in agreement with the structure of the title compound.

Intramolecular metathesis of a vinyl group with vinylidene C=C double bond in Ru complexes.

The cationic complex {[Ru]=C=CHCPh2CH2CH=CH2}BF4 (3a, [Ru] = (eta5-C5H5)(PPh3)2Ru) in solution transforms to {[Ru]=C=CHCH2CPh2CH=CH2}BF4 (4a) via a new metathesis process of the terminal vinyl group with the C=C of the vinylidene group which is confirmed by 13C labeling studies. This transformation is irreversible as revealed by deuteration and decomplexation studies. The cationic complex {[Ru]=C=CHCPh2CH2CMe=CH2}BF4 (3b) undergoes a cyclization process yielding 6b containing a eta2-cyclic allene ligand which is fully characterized by single-crystal X-ray diffraction analysis. Analogous complexes 4a' and 6b' ([Ru] = (eta5-C5H5)(dppe)Ru) containing dppe ligands were similarly obtained from protonation of the corresponding acetylide complexes via formation of vinylidene intermediate. Protonation of the acetylide complex containing a terminal alkynyl group [Ru]-CCCPh2CH2CCH (2c) generates the vinylidene complex {[Ru]=C=CHCPh2CH2CCH}BF4 (3c) which again undergoes an irreversible transformation to give {[Ru]=C=CHCH2CPh2CCH}BF4 (4c) possibly via a pi-coordinated alkynyl complex followed by hydrogen and metal migration. No similar transformation is observed for the analogous dppe complex 3c'. With an extra methylene group, complex {[Ru]=C=CHCPh2CH2CH2CH=CH2}BF4 (3d) and complex {[Ru]=C=CHCPh2CH2Ph}BF4 (3e) are stable. The presence of a gem-diphenylmethylene moiety at the vinylidene ligand with the appropriate terminal vinyl or alkynyl group along with the correct steric environment implements such a novel reactivity in the ruthenium vinylidene complexes.