A highly diastereo- and enantioselective BOX/Cu(II)-catalyzed C2,C3-cyclopentannulation of indoles with donor–acceptor cyclopropanes has been developed on the basis asymmetric formal [3 + 2] cycloaddition indoles. This reaction provides rapid facile access to a series enantioenriched cyclopenta-fused indoline products can be further extended construction tetracyclic pyrroloindolines. The synthetic potential was demonstrated in four-step synthesis core structure borreverine.

Iridium catalyzed alkyne hydroboration with o-carborane cage B-H has been achieved, leading to the formation of a series 4-B-alkenylated-o-carborane derivatives in high yields excellent regioselectivity via direct bond activation. In this reaction carboxy group is used as traceless directing group, which removed during one-pot process. After confirmation key intermediate, possible mechanism proposed, involving tandem sequence Ir-mediated activation, insertion, protonation, and decarboxylation.

ConspectusCarboranes are a class of polyhedral carbon-boron molecular clusters featuring three-dimensional aromaticity, which often considered as 3D analogues benzene. Their unique structural and electronic properties make them invaluable building blocks for applications ranging from functional materials to versatile ligands pharmaceuticals. Thus, selective functionalization carboranes has received tremendous research interest. In earlier days, the vast majority works in this area were...

A new class of organic−inorganic hybrid compounds bearing a cyclic π-ligand, an icosahedral carborane moiety, and bridging group has been developed. These are very versatile ligands, featuring both organic inorganic moiety as well ligand. They can be readily converted into mono-, di-, tri- pentaanionic species under suitable reaction conditions, leading to the generation organometallic in which carboranyl unit cast role bulky substituent, σ-, η5, η6, or η7 π-ligand. This Account provides...

The crystal structure of the tri-isopropyl silyl species, i-Pr(3)Si(Br(6)-CB(11)H(6)), where brominated carborane Br(6)-CB(11) H(6)(-) is perhaps least nucleophilic anion presently known, has revealed highest degree silylium cation character (R(3)Si(+)) yet observed. average C-Si-C angle 117 degrees , only 3 short planarity expected a pure ion(120 ). This value compares to 114 recently reported for toluene-solvated cation, [Et(3)Si(toluene)](+) by Lambert and co-workers. greater ion...

All zipped up: Titanium complexes are designed as efficient catalysts for the copolymerization of ethylene with polar olefins, such ω-alkenol and ω-alkenoic acid. An organophosphine catalyst can be zippered on polyethylene (see scheme; TBS=tert-butyldimethylsilyl, FG=functional group, MMAO=modified methylaluminoxane) to form an recoverable initiator [3+2] cycloaddition.

Transition metal catalyzed regioselective amination of the cage B(4)–H bond in o-carboranes has been achieved for first time using O-benzoyl hydroxylamines or organic azides as reagents, leading to preparation a series tertiary and secondary carboranyl amines. Both reactions proceeded under mild conditions without addition any external oxidants. Hydrogenolysis resultant product 4-N(CH2Ph)2-o-carborane afforded primary amine, 4-amino-o-carborane, quantitative yield.

Abstract Carboranes are carbon–boron molecular clusters, which can be viewed as three-dimensional analogues to benzene. They finding many applications in medicine, materials and organometallic chemistry. On the other hand, their exceptional thermal chemical stabilities, well 3D structures, make them very difficult functionalized, particular regioselective functionalization of BH vertex among ten similar B–H bonds. Here we report a efficient iridium-catalysed borylation cage B(3,6)–H bonds o...

Beverly Hills copper(II): A highly efficient catalytic asymmetric Nazarov reaction has been developed through control of the enantioselectivity cyclization step, affording chiral O-heterohexahydroindenones in excellent yields with and diastereoselectivity. HFIP=hexafluoro-2-propanol, BArF= tetrakis[3,5-bis(trifluoromethyl)phenyl] borate.

Abstract Carboranes are a class of carbon–boron molecular clusters with unusual thermal and chemical stabilities. They have been proved as very useful building blocks in supramolecular design, optoelectronics, nanomaterials, boron neutron capture therapy agents organometallic/coordination chemistry. Thus, the functionalization o ‐carboranes has received growing interests. Over past decades, most works this area focused on cage carbon weakly acidic C−H proton can be readily deprotonated by...

A Pd(II)-catalyzed direct selective fluorination reaction of carboranes using a F+ reagent has been developed, leading to series polyfluorocarboranes in high isolated yields. The mechanism involving electrophilic B–H activation, oxidation Pd(II) by species, and reductive elimination is proposed.

New 6,13-bis[1'-(C≡C)-2'-R-1',2'-C2B10H10]pentacenes (R = H, Me, Et, n-Bu) are synthesized and fully characterized. The results show that the alkyl substituents on second cage carbon have a significant impact molecular packing, incorporation of o-carboranyl moiety into π conjugated system can lower both LUMO HOMO energy levels, converting typical p-type semiconductor an ambipolar one.

Abstract Palladium‐catalyzed intermolecular coupling of o ‐carborane with aromatics by direct cage B−H bond activation has been achieved, leading to the synthesis a series B(4,5)‐diarylated‐ ‐carboranes in high yields excellent regioselectivity. Traceless directing group ‐COOH plays crucial role for site‐ and di‐selectivity such reaction. A Pd II –Pd IV catalytic cycle is proposed be responsible stepwise arylation.

Abstract Palladium‐catalyzed direct dialkenylation of cage B(4,5)H bonds in o ‐carboranes has been achieved with the help a carboxylic acid directing group, leading to preparation series 4,5‐[trans‐(ArCHCH)] 2 ‐ocarboranes high yields excellent regioselectivity. The traceless eliminated during course reaction, is responsible for controlling regioselectivity and dialkenylation. A possible catalytic cycle proposed, involving tandem sequence Pd II ‐initiated BH activation, alkene insertion,...

Carboranes are a class of polyhedral boron hydride clusters in which one or more the BH vertices replaced by CH units. Their chemistry has been dominated 12-vertex carboranes for over half century. In contrast, knowledge regarding supercarboranes (carboranes with than 12 vertices) had limited merely to possible cage geometries predicted theoretical work before 2003. Only recent years significant progress made synthesizing supercarboranes. Such breakthrough relied on use Carbon-Atoms-Adjacent...

Abstract A rhodium‐catalyzed hydroxylation of a cage B4−H bond in o ‐carboranes with either O 2 or air as the oxygen source is described, and serves new methodology for regioselective generation series 4‐OH‐ one‐pot process. The use both oxidant makes this protocol very environmentally friendly practical.

A borylene cation stabilized by bis(silylene) and carbon monoxide was prepared structurally characterized via the reaction of bis(silylene)-stabilized bromoborylene with W(CO)6. This is first example a coordinated three neutral ligands, which can be viewed as cationic form long-sought Lewis base-stabilized zerovalent boron compound. cleave dihydrogen.

Palladium-catalyzed direct intermolecular coupling of <italic>o</italic>-carboranes with alkynyl bromides or terminal alkynes has been achieved, for the first time, help a traceless directing group –COOH, leading to synthesis series new cage B(4)-alkynylated-<italic>o</italic>-carboranes in high yields excellent regioselectivity.

A highly diastereoselective and enantioselective Cu(II)/SaBOX-catalyzed [2 + 2] cycloaddition of methylidenemalonate multisubstituted alkenes was developed to furnish optically active cyclobutanes in high yields with >99/1 dr up >99% ee. By application the newly method, total synthesis (+)-piperarborenine B completed eight steps from olefin 17% overall yield 99%

Abstract Carboranes are a class of carbon-boron molecular clusters, possessing extraordinary characteristics including three-dimensional aromaticity conjugated by σ-bonds, icosahedral geometry and inherent robustness. They finding growing applications as valuable building blocks in boron neutron capture therapy agents, pharmacophores, nanomaterials, optoelectronic, organometallic/coordination chemistry more. Therefore, the effective controlled functionalization carboranes has attracted...

An efficient Pd-catalyzed regioselective intramolecular aerobic oxidative dehydrocoupling of BH/CH between o-carborane and arenes has been achieved with the construction a series five-, six- seven-membered rings under mild reaction conditions. Control experiments indicate that B-H activation proceeds preferentially over aryl C-H. These new polyarene-carborane conjugates have potential applications in materials as demonstrated by pyrene fused exhibits unique dual-phase emission, charge...