A radical process towards the development of transition-metal-free aromatic carbon-carbon bond-forming reactions.

Transition-metal-free cross-coupling reactions have been a hot topic in recent years. With the aid of a radical initiator, a number of unactivated arene C-H bonds can be directly arylated/functionalized by using aryl halides through homolytic aromatic substitution. Commercially available or specially designed promoters (e.g. diamines, diols, and amino alcohols) have been used to make this synthetically attractive method viable. This protocol offers an inexpensive, yet efficient route to aromatic C-C bond formations since transition metal catalysts and impurities can be avoided by using this reaction system. In this article, we focus on the significance of the reaction conditions (e.g. bases and promoters), which allow this type of reaction to proceed smoothly. Substrate scope limitations and challenges, as well as mechanistic discussion are also included.

Synthesis and structure of metallacarboranes bearing carborane-fused cyclopentenyl and dicarbollyl-fused cyclopentene ligands.

New types of ligands, carborane-fused cyclopentenyl and dicarbollyl-fused cyclopentene, were conveniently prepared in high yields. Treatment of the lithium salt of carborane-fused cyclopentenyl anion, [1,2-[C(Me)CHC(Ph)]-1,2-C2B10H10]Li, with [Cp*RuCl]4 generated an 18-electron complex [η3:η2-(PhCCHCMe)C2B10H10]Ru(η5-Cp*). On the other hand, reaction of the dicarbollide salt, [7,8-(CH2CH[double bond, length as m-dash]CMe)-7,8-C2B9H9]Na2 with [(η6-p-cymene)RuCl2]2 or CoCl2/CpNa, afforded the salt metathesis product [η5-(CH2CH[double bond, length as m-dash]CMe)C2B9H9]Ru(η6-p-cymene) or [η5-(CH2CH[double bond, length as m-dash]CMe)C2B9H9]Co(η5-C5H5) in good yields. In contrast, [7,8-(CH2CH[double bond, length as m-dash]CMe)-7,8-C2B9H9]Na2 reacted with Ni(dppp)Cl2 (dppp = 1,3-bis(diphenylphosphino)propane) to give another 18-electron metallacarborane [η5-(CH2CH[double bond, length as m-dash]CMe)C2B9H9]Ni(dppp), in which one of the cage carbon atoms has been isomerized to the lower belt of the cage due to steric reasons. All these new metallacarborane compounds were fully characterized by NMR spectroscopy, high-resolution mass spectroscopy and single-crystal X-ray analyses.

Cyclic amino(carboranyl) silylene: synthesis, structure and reactivity.

A carbene-stabilized cyclic amino(carboranyl) silylene has been prepared from the reaction of cyclic amino(carboranyl) chlorosilane with N-heterocyclic carbene via HCl elimination. Its structure has been characterized by single-crystal X-ray analysis and DFT calculations. It is a very strong σ donor and relatively poor π acceptor. It can form a Lewis acid-base adduct with borane and undergo cycloaddition reactions with unsaturated molecules such as diphenylacetylene and benzophenone.

Synthesis, structure and aromaticity of carborane-fused carbo- and heterocycles.

Conjugation between a 3-D icosahedral carborane and a fused 2-D π-ring system is ambiguous. To address this issue, we prepared several carborane-fused carbo- and heterocycles. Detailed studies on their molecular structures, NMR data, and NICS (nucleus-independent chemical shift) and ISE (isomerization stabilization energy) values as well as molecular orbital analyses clearly suggest the presence of (1) considerable aromatic character in the exo five-membered ring of carborane-fused carbo- and heterocycles and (2) considerable conjugation between a 3-D carborane and a fused 2-D π-ring system. These results will shed some light on the design of new carborane-based materials.

The synthesis, structure and reactivity of an imine-stabilized carboranylphosphorus(i) compound.

A new imine-stabilized carboranyl-phosphinidene has been synthesized and structurally characterized. DFT studies suggest that the imine moiety provides an electron pair to stabilize carboranyl-phosphinidene. On the other hand, the sterically demanding carboranyl ligand can prevent the dimerization, facilitating the formation of monomeric phosphinidene. These observations are supported by the reactivity studies. Such a monovalent phosphorous(i) compound can undergo reactions with Cu(OAc)2, S, Se, (TMS)CHN2 and HCl to give various phosphorus(iii) species. All compounds are fully characterized by NMR spectroscopy, elemental analyses as well as single-crystal X-ray analyses.

Intramolecular direct C-H bond arylation from aryl chlorides: a transition-metal-free approach for facile access of phenanthridines.

A C-H arylation with aryl chloride is made viable through a transition-metal-free approach. In the presence of a simple diol associating with KOt-Bu, various phenanthridine derivatives can be conveniently accessed. In particular, only 10 mol % of simple and inexpensive ethylene glycol is required for this protocol. These results represent the first general examples of aryl chloride/C-H coupling under transition-metal-free conditions.