Regioselective trans-Carboboration of Propargyl Alcohols

Proper choice of the base allowed trans-diboration of propargyl alcohols with B2(pin)2 to evolve into an exquisitely regioselective procedure for net trans-carboboration. The method is modular as to the newly introduced carbon substituent (aryl, methyl, allyl, benzyl, alkynyl), which is invariably placed distal to the −OH group

Hydrogenative Cyclopropanation and Hydrogenative Metathesis

The unusual geminal hydrogenation of a propargyl alcohol derivative with [CpXRuCl] as the catalyst entails formation of pianostool ruthenium carbenes in the first place; these reactive intermediates can be intercepted with tethered alkenes to give either cyclopropanes or cyclic olefins as the result of a formal metathesis event. The course of the reaction is critically dependent on the substitution pattern of the alkene trap

A Gold-Catalyzed Entry into the Sesquisabinene and Sesquithujene Families of Terpenoids and Formal Total Syntheses of Cedrene and Cedrol

A concise entry into the bicyclic cyclopropyl ketone derivatives 5 and 6 by way of a gold-catalyzed Ohloff–Rautenstrauch-type enyne cycloisomerization is described. The required substrates were prepared by an asymmetric addition of the branched allylzinc reagent 21 to the alkynyl aldehyde 17 mediated by the deprotonated bisoxazoline (BOX) ligand 22. Compounds 5 and 6 were then converted into a host of different members of the sesquisabina- and sesquithuja families of terpenoids, inter alia with the aid of iron-catalyzed cross-coupling reactions. As the relative and absolute configuration of 5 and 6 could be unambiguously established, the synthetic samples allowed the previously unknown stereostructures of various such terpenoids to be unraveled, including cis-sesquisabinene hydrate (33), 7-epi-sesquithujene (36), sesquisabinene B (37) and epoxy-sesquithujene (45). Moreover, the preparation of 6 also constitutes a formal total synthesis of cedrene (11) and cedrol (12)

The Triple-Bond Metathesis of Aryldiazonium Salts: A Prospect for Dinitrogen Cleavage

The {N2} unit of aryldiazonium salts undergoes unusually facile triple-bond metathesis on treatment with molybdenum or tungsten alkylidyne ate complexes endowed with triphenylsilanolate ligands. The reaction transforms the alkylidyne unit into a nitrile and the aryldiazonium entity into an imido ligand on the metal center, as unambiguously confirmed by X-ray structure analysis of two representative examples. A tungsten nitride ate complex is shown to react analogously. Since the bonding situation of an aryldiazonium salt is similar to that of metal complexes with end-on-bound dinitrogen, in which {N2}→M σ donation is dominant and electron back donation minimal, the metathesis described herein is thought to be a conceptually novel strategy toward dinitrogen cleavage devoid of any redox steps and, therefore, orthogonal to the established methods

Catalysis-Based Total Synthesis of Putative Mandelalide A

A concise synthesis of the putative structure assigned to the highly cytotoxic marine macrolide mandelalide A (1) is disclosed. Specifically, an iridium-catalyzed two-directional Krische allylation and a cobalt-catalyzed carbonylative epoxide opening served as convenient entry points for the preparation of the major building blocks. The final stages feature the first implementation of terminal-acetylene metathesis into natural product synthesis, which is remarkable as this class of substrates was beyond reach until very recently; key to success was the use of the highly selective molybdenum alkylidyne complex 42 as the catalyst. Although the constitution and stereochemistry of the synthetic samples are unambiguous, the spectra of 1 as well as of 11-epi-1 deviate from those of the natural product, which implies a subtle but deep-seated error in the original structure assignment