Covering: 1973 to 2013 The biological activities of tigliane, lathyrane, ingenane, casbane, jatropholane and premyrsinane diterpenoids which contain the gem-dimethylcyclopropyl unit are described. Particular attention is given to their anti-viral, anti-microbial and cytotoxic activities. In the main text there are 132 references. The electronic supplementary information contains tables listing 424 of these diterpenoids, their occurrence and biological activity together with the references.

Covering: 1963 up to the end of 2014 The biological activities of aristolane, aromadendrane, ent-1,10-secoaromadendrane, 2,3-secoaromadendrane, ent-5,10-cycloaromadendrane, bicyclogermacrene, lepidozane, and maaliane terpenoids which contain the gem-dimethylcyclopropyl unit are described. Particular attention is given to their anti-viral, anti-microbial and cytotoxic activities. In the main text there are 119 references covering the literature from 1963–2014. The ESI contains tables listing 332 of these terpenoids, their occurrence and biological activity together with the related references.

A novel diterpenoid, gaditanone (2), which possesses an unprecedented 5/6/4/6-fused gaditanane tetracyclic ring skeleton, and a new jatrophane (1) were isolated from the aerial parts of Euphorbia gaditana. The chemical structures and absolute configurations were determined by extensive spectroscopic NMR studies and ECD data analysis. A proposed biosynthetic pathway is presented for compound 2.

A small library of phorbol 12,13-diesters bearing low lipophilicity ester chains was prepared as potential neurogenic agents in the adult brain. They were also used in a targeted UHPLC–HRMS screening of the latex of Euphorbia resinifera. Two new 12-deoxy-16-hydroxyphorbol 13,16-diesters were isolated, and their structures were deduced using two-dimensional NMR spectroscopy and NOE experiments. The ability of natural and synthetic compounds to stimulate transforming growth factor alpha (TFGα) release, to increase neural progenitor cell proliferation, and to stimulate neurogenesis was evaluated. All compounds that facilitated TGFα release promoted neural progenitor cell proliferation. The presence of two acyloxy moieties on the tigliane skeleton led to higher levels of activity, which decreased when a free hydroxyl group was at C-12. Remarkably, the compound bearing isobutyryloxy groups was the most potent on the TGFα assay and at inducing neural progenitor cell proliferation in vitro, also leading to enhanced neurogenesis in vivo when administered intranasally to mice.

The complex [Cp*RuCl(COD)] reacts with LH₂Cl₂ (L = bis(3-methylimidazol-2-ylidene)) and LiBuⁿ in tetrahydrofuran at 65 °C furnishing the bis-carbene derivative [Cp*RuCl(L)] (2). This compound reacts with NaBPh₄ in MeOH under dinitrogen to yield the labile dinitrogen-bridged complex [{Cp*Ru(L)}₂(μ-N₂)][BPh₄]₂ (4). The dinitrogen ligand in 4 is readily replaced by a series of donor molecules leading to the corresponding cationic complexes [Cp*Ru(X)(L)][BPh₄] (X = MeCN 3, H₂6, C₂H₄8a, CH₂CHCOOMe 8b, CHPh 9). Attempts to recrystallize 4 from MeNO₂/EtOH solutions led to the isolation of the nitrosyl derivative [Cp*Ru(NO)(L)][BPh₄]₂ (5), which was structurally characterized. The allenylidene complex [Cp*Ru═C═C═CPh₂(L)][BPh₄] (10) was also obtained, and it was prepared by reaction of 2 with HC≡CC(OH)Ph₂ and NaBPh₄ in MeOH at 60 °C. Complexes 3, 4, and 6 are efficient catalyst precursors for the transfer hydrogenation of a broad range of ketones. The dihydrogen complex 6 has proven particularly effective, reaching TOF values up to 455 h^–1 at catalyst loadings of 0.1% mol, with a high functional group tolerance on the reduction of a broad scope of aryl and aliphatic ketones to yield the corresponding alcohols.

^† These authors contributed equally to this work This short review aims to provide an overview of the use of Cp₂Ti(III)Cl and other related titanocene(III) species as coordinating reagents­ in template reactions in the selective preparation of C–C and C–O bonds. These complexes are able to assemble two components to produce powerful reactions possessing high regio-, chemo-, diastereo-, and enantioselectivity. The titanocene templates are divided into five structural types. The chemical transformations by these valuable templates, the substrate scope and mechanistic insights will also be described. 1 Introduction 2 Precedents for the Coordination of Ti(III) Species to Heteroatoms 2.1 Coordination of Compounds with Hydrogen–Heteroatom Bonds to Ti(III) Species 2.2 Coordination of Halogens to Ti(III) Species 3 Types of Titanocene Templates 4 Template Type I Mediated Organic Reactions 4.1 Methylenecyclopropanation of Allylic Alcohols 4.2 Base-Free O-Acylation of Alcohols and Phenol 4.3 Epoxidation of Allylic Alcohols 5 Template Type II Mediated Organic Reactions 5.1 Ketone–Nitrile Cross-Coupling Reactions 5.2 Imine–Nitrile Cross-Coupling Reactions 5.3 Reductive Alkylation of Enones with Activated Alkenes 6 Template Type III Mediated Organic Reactions 6.1 Pinacol Coupling of Ketones 7 Template Type IV Mediated Organic Reactions 7.1 Michael-Type Addition of Aldehydes to Conjugated Enals 7.2 Allylation, Crotylation, and Prenylation 7.3 Barbier-Type Progargylation and Allenylation 8 Template Type V Mediated Organic Reactions 8.1 Protection of Alcohols as 2-O-THF and 2-O-THP Ethers 8.2 Pinacol Coupling of Aldehydes 8.3 McMurry Couplings 9 Conclusions and Perspectives