Synthetic studies towards the novel diterpenoid rameswaralide: RCM mediated acquisition of the tricyclic core

A synthetic approach towards the novel anti-inflammatory diterpenoid rameswaralide from the cis-Corey lactone involving a tandem RCM and Diels-Alder reaction has been conceived and endeavors so far have led to the acquisition of the BCD ring fragment of the natural product.     

Quest for inosito-inositols: synthesis of novel, annulated and conformationally locked inositols

A new family of annulated inositols (inosito-inositols) has been conceptualized. Naphthalene has been elaborated into novel cyclohexa-annulated neo- and chiro-inositols, with two additional hydroxyl functionalities, through a series of stereoselective oxyfunctionalization protocols. The trans-ring fusion present in these new annulated inositols ensures conformational locking.     

Enantioselective total synthesis of epoxyquinone natural products (−)-phyllostine, (+)-epoxydon, (+)-epiepoxydon and (−)-panepophenanthrin: access to versatile chiral building blocks through enzymatic kinetic resolution

A new enzyme mediated protocol to access versatile chiral building blocks for the synthesis of epoxyquinone natural products is delineated. Total syntheses of (−)-phyllostine, (+)-epoxydon, (+)-epiepoxydon and (−)-panepophenanthrin have been accomplished to demonstrate the efficacy of this approach.     

Towards an enantiospecific total synthesis of garsubellin A and related phloroglucin natural products: the α-pinene approach

The first enantiospecific approach to garsubellin A and related phloroglucin natural product nemorosone, of contemporary interest from (−)-α-pinene, has been delineated. Through a series of stereospecific operations, the requisite stereochemistry of the prenyl groups has been secured. Kende cyclization has been employed as the key step to construct the functionalized bicyclo[3.3.1]nonane core.     

Enantioselective total synthesis of polyoxygenated cyclohexanoids: (+)-streptol, ent-RKTS-33 and putative ‘(+)-parasitenone’. Identity of parasitenone with (+)-epoxydon

Short, simple and enantioselective syntheses of the natural product (+)-streptol, the non-peptide apoptosis inhibitor ent-RKTS-33 and the putative structure of ‘parasitenone’ have been accomplished from the readily available chiral building block. ‘Parasitenone’ has been shown to be identical with the known natural product epoxydon.     

Studies towards the total synthesis of novel dolabellane-type diterpenoids: construction of the 5,11-fused bicyclic framework

An oxy-Cope protocol has been grafted on to a previously crafted hydroazulenic system to provide a facile entry into the 5,11-fused bicyclic skeleton present in the novel neodolabellane diterpenoids. Formation of a novel tricyclic diterpenoid framework, generated through a transannular cyclization in the 11-membered ring present in the neodolabellane skeleton and embodying a bridged cycloheptatriene moiety, has also been encountered.     

Enantioselective total synthesis of (+)-panepophenanthrin, a novel inhibitor of the ubiquitin-activating enzyme

An enantioselective total synthesis of the novel natural product (+)-panepophenanthrin has been accomplished in which a biomimetic Diels-Alder dimerisation is a key step. The monomeric precursor 2 was assembled from the readily available Diels-Alder adduct of cyclopentadiene and p-benzoquinone through a short, simple sequence employing chemo- and stereoselective operations.     

Blocking the Hype-Hypocrisy-Falsification-Fakery Pathway is Needed to Safeguard Science

In chemistry and other sciences, hype has become commonplace, compounded by the hypocrisy of those who tolerate or encourage it while disapproving of the consequences. This reduces the credibility and trust upon which all science depends for support. Hype and hypocrisy are but first steps down a slippery slope towards falsification of results and dissemination of fake science. Systemic drivers in the contemporary structure of the science establishment encourage exaggeration and may lure the individual into further steps along the hype-hypocrisy-falsification-fakery continuum. Collective, concerted intervention is required to effectively discourage entry to this dangerous pathway and to restore and protect the probity and reputation of the science system. Chemists must play and active role in this effort.