Owing to its tremendous preparative importance, rhodium carbene chemistry has been studied extensively during past decades. The invoked intermediates have, however, so far proved too reactive for direct inspection, and reliable experimental information has been extremely limited. A series of X-ray structures of pertinent intermediates of this type, together with supporting spectroscopic data, now closes this gap and provides a detailed picture of the constitution and conformation of such species. All complexes were prepared by decomposition of a diazoalkane precursor with an appropriate rhodium source; they belong to either the dirhodium(II) tetracarboxylate carbene series that enjoys widespread preparative use, or to the class of mononuclear half-sandwich carbenes of Rh(III), which show considerable potential. The experimental data correct or refine previous computational studies but corroborate the currently favored model for the prediction of the stereochemical course of rhodium catalyzed cyclopropanations, which is likely also applicable to other reactions. Emphasis is put on stereoelectronic rather than steric arguments, with the dipole of the acceptor substituent flanking the carbene center being the major selectivity determining factor. Moreover, the very subtle influence exerted by the anionic ligands on a Rh(III) center on the chemical character of the resulting carbenes species is documented by the structures of a homologous series of halide complexes. Finally, the isolation of a N-bonded Rh(II) diazoalkane complex showcases that steric hindrance represents an inherent limitation of the chosen methodology.

The marine natural products amphidinolide C (1) and F (4) differ in their side chains but share a common macrolide core with a signature 1,4-diketone substructure. This particular motif inspired a synthesis plan predicating a late-stage formation of this non-consonant ("umpoled") pattern by a platinum-catalyzed transannular hydroalkoxylation of a cycloalkyne precursor. This key intermediate was assembled from three building blocks (29, 41 and 47 (or 65)) by Yamaguchi esterification, Stille cross-coupling and a macrocyclization by ring-closing alkyne metathesis (RCAM). This approach illustrates the exquisite alkynophilicity of the catalysts chosen for the RCAM and alkyne hydroalkoxylation steps, which activate triple bonds with remarkable ease but left up to five other π-systems in the respective substrates intact. Interestingly, the inverse chemoselectivity pattern was exploited for the preparation of the tetrahydrofuran building blocks 47 and 65 carrying the different side chains of the two target macrolides. These fragments derive from a common aldehyde precursor 46 formed by an exquisitely alkene-selective cobalt-catalyzed oxidative cyclization of the diunsaturated alcohol 44, which left an adjacent acetylene group untouched. The northern sector 29 was prepared by a two-directional Marshall propargylation strategy, whereas the highly adorned acid subunit 41 derives from D-glutamic acid by an intramolecular oxa-Michael addition and a proline-mediated hydroxyacetone aldol reaction as the key steps; the necessary Me3 Sn-group on the terminus of 41 for use in the Stille coupling was installed via enol triflate 39, which was obtained by selective deprotonation/triflation of the ketone site of the precursor 38 without competing enolization of the ester also present in this particular substrate.

For the first time, the stereochemical course of an asymmetric cyclopropanation can be discussed on the basis of experimental structural information on a pertinent chiral dirhodium carbene intermediate. Key to success was the formation of racemic single crystals of a heterochiral [Rh₂{(S*)-PTTL}₄{=C(Ar)COOMe}][Rh₂{(R*)-PTTL}₄] (Ar=MeOC₆H₄; PTTL=N-phthaloyl-tert-leucinate) capsule, which has been characterized by X-ray diffraction. NMR spectroscopic data confirm that the obtained structural portrait is also relevant in solution and provide additional information about the dynamics of this species. The chiral binding pocket is primarily defined by the conformational preferences of the N-phthaloyl-protected amino acid ligands and reinforced by a network of weak interligand interactions that get stronger when chlorinated phthalimide residues are used

Traditional rhodium carbene chemistry relies on the controlled decomposition of diazo derivatives with [Rh(OAc)] or related dinuclear Rh(+2) complexes, whereas the use of other rhodium sources is much less developed. It is now shown that half-sandwich carbene species derived from [Cp*MX] (M = Rh, Ir; X = Cl, Br, I, Cp* = pentamethylcyclopentadienyl) also exhibit favorable application profiles. Interestingly, the anionic ligand X proved to be a critical determinant of reactivity in the case of cyclopropanation, epoxide formation and the previously unknown catalytic metathesis of azobenzene derivatives, whereas the nature of X does not play any significant role in -OH insertion reactions. This perplexing disparity can be explained on the basis of spectral and crystallographic data of a representative set of carbene complexes of this type, which could be isolated despite their pronounced electrophilicity. Specifically, the donor/acceptor carbene 10a derived from ArC(═N)COOMe and [Cp*RhCl] undergoes spontaneous 1,2-migratory insertion of the emerging carbene unit into the Rh-Cl bond with formation of the C-metalated rhodium enolate 11. In contrast, the analogous complexes 10b,c derived from [Cp*RhX] (X = Br, I) as well as the iridium species 13 and 14 derived from [Cp*IrCl] are sufficiently stable and allow true carbene reactivity to be harnessed. These complexes are competent intermediates for the catalytic metathesis of azobenzene derivatives, which provides access to α-imino esters that would be difficult to make otherwise. Rather than involving metal nitrenes, the reaction proceeds via aza-ylides that evolve into diaziridines; a metastable compound of this type has been fully characterized.

Complexes of type [{R2P(CH2) n PR2}Ru(2-Me-all)2] (2-Me-all = 2-methylpropenyl; R = Cy, n = 1−3, 5a−c; R = Me, n = 2, 6; R2 = −(CH2)4−, n = 2, 7) have been synthesized from the reaction of the corresponding electron-rich diphosphines with [(cod)Ru(2-Me-all)2] (4) at 50−70 °C. The new complexes were fully characterized by multinuclear NMR spectroscopy and mass spectroscopic techniques. Reacting 4 with Cy2P(CH2) n PCy2 containing hydrocarbon bridges with n = 3 (1c) and n = 4 (1d) at 95 and 50 °C, respectively, led to [κ2P,P‘-{(η3-C6H8)CyP(CH2) n PCy2}Ru(η3-C8H13)] (n = 3, 4; 8c,d) via intramolecular C−H bond activation and concomitant hydride transfer to cyclooctadiene. The molecular structure of 8c was unambiguously assigned by multinuclear 1D and 2D NMR spectroscopy and confirmed by single-crystal X-ray diffraction. The new complexes were tested as homogeneous catalyst precursors in thermal intermolecular C−H activation processes. In dehydrogenation of cyclooctane (coa), an initial turnover frequency of 1.9 h-1 was observed using complex 5a under refluxing conditions without the need of a hydrogen scavenger. A maximum total number of 5 catalytic turnovers was achieved after 48 h. Ligand degradation by dehydrogenation was detected under catalytic conditions, presumably initiated via intramolecular C−H activation as in species of type 8. Attempts to utilize complexes 5 for C−H activation in scCO2 as the reaction medium resulted in insertion of CO2 into the Ru−allyl moiety, yielding catalytically inactive ruthenium carboxylates.