Construction of a Metallacyclopentadiene Ring through the Attack of Carbanions to M≡C Bond Followed by C—H Activation

Metallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions,therefore,new methods to achieve them are anticipated.In this study,a formal[3+2]method,through the reactions of an osmapentalyne with benzyl carbanions,was developed.The reactions underwent a nucleophilic attack of carbanions to the Os≡C bond,followed by C—H activation to form the five-membered osmacyclopentadiene ring.Most of the reactions were carried out at room temperature,the substituents on the aromatic rings of benzyl carbanions are diverse,and the resulting products contain an Os—H bond,representing a novel type of 10C-carbolong complexes.This work provides a new convenient route to construct metallacyclopentadienes,which is expected to further promote the development of such a type of substances.

Formal[2+1]Cycloadditions of a Metallacyclopentadiene Unit with Alkynes:Constructing Tetracyclic Conjugated Frameworks with Bridgehead Metals

Comprehensive Summary Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes.Though versatile reactions of metallacyclopentadienes with alkynes have been disclosed,[2+1]cycloadditions of metallacyclopentadienes and alkynes have never been discovered.In present work,we report the formal[2+1]cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes,providing a facile strategy to construct tetracyclic conjugated compounds.The deuterated experiment indicates a metal vinylidene intermediate has been involved in[2+1]cycloaddition.Moreover,the electrophilic substitution reaction of the tetracyclic conjugated compound with the aid of density functional theory(DFT)calculated Fukui functions is investigated.

The First OCCCO Pentadentate Chelates:Osmium Mediated Stepwise Oxidations of Terminal Alkynes by Pyridine N-Oxide

of main observation and conclusion Oxygen atom transfer reactions between alkynes and heteroarene N-oxides are currently mediated by transition metal,such as gold,ruthenium or rhodium,but they have never been catalyzed by osmium.Herein,we report stepwise oxidations of terminal alkynes mediated by an osmium carbolong complex,using pyridine N-oxide as the oxidant,yielding novel aldehyde-or carboxylic acid-coordinated osmapentalyne derivatives selectively.The mechanism was illustrated by density functional theory calculations,providing a new route for oxygen atom transfer between heteroarene N-oxides and alkynes.

A One-Pot Strategy for the Synthesis of β-Substituted Rhoda-and Irida-Carbolong Complexes

Comprehensive Summary Starting from an organic multiyne,three steps are normally needed for the preparation of non-βphosphonium functionalized rhodaand irida-carbolong complexes.Herein,a one-pot strategy,by mixing a multiyne,a nucleophile,and Rhcl(CO)(PPh_(3))_(2)/AgBF_(4)or[Ir(CH:CN)(CO)(PPh_(3))_(2)]BF_(4),was developed to achieve a series ofβfunctionalized rhoda-and irida-carbolong complexes.Theβ-substituents in these complexes can be various C-,N-and O-centered groups,dependent on the nucleophiles used.This strategy provides a new convenient route to construct carbolong complexes,which is important for the further development of carbolong chemistry.

Carbolong Chemistry: Planar CCCCX-Type (X = N, O, S) Pentadentate Chelates by Formal [3+1] Cycloadditions of Metalla-Azirines with Terminal Alkynes

Three-membered unsaturated rings have been widely utilized in organic synthesis due to their inherent highly strained structures.Although much research has been applied to ring-expansion reactions of such strained ring systems,pathways other than[3+2]cycloadditions have rarely been observed in their reactions with alkynes,and to date,no[3+1]cycloadditions of isolated three-membered unsaturated rings with alkynes have been reported.Here we demonstrate an unprecedented[3+1]cycloaddition in which a fused metalla-azirine is used as a template to generate a series of planar CCCCX-type(X=N,O,S)pentadentate carbolong complexes 3–6.A series of substituted alkynes was tested for further exploration of the scope and mechanism for the[3+1]cycloaddition reactions.Complexes 3–6 represent rare examples of planar pentadentate complexes that assemble fourπ-conjugated fused rings by one bridgehead atom.These novel complexes are thermally stable in air and absorb ultraviolet,visible,and near-infrared light,and thus are potentially applicable in photoelectric devices and pharmaceuticals.