Biosynthesis and Chemical Synthesis of Presilphiperfolanol Natural Products

Abstract

Presilphiperfolanols constitute a family of biosynthetically important sesquiterpenes that can rearrange to diverse sesquiterpenoid skeletons. While the origin of these natural products can be traced to simple linear terpene precursors, the details of the enzymatic cyclization mechanism that form the stereochemically dense tricyclic skeleton have required extensive biochemical, computational, and synthetic investigation. Parallel efforts to prepare the unique and intriguing structures of these compounds by total synthesis have also inspired novel strategies, resulting in two synthetic approaches and two completed syntheses. While the biosynthesis and chemical synthesis studies performed to date have provided much insight into the role and properties of these molecules, new questions regarding the biosynthesis of newer members of the family and subtle details of the cyclization mechanism have yet to be explored.

Expedient and Diastereodivergent Assembly of Terpenoid Decalin Subunits having Quaternary Stereocenters through Organocatalytic Robinson Annulation of Nazarov Reagent

“…We then undertook as ystematic investigation of bifunctionalt hiourea and squaramide organocatalysts, because of their commanding performance in asymmetric Michael addition reactions. However,v ariation of the thiourea moiety of the catalyst with more acidic double hydrogen-bond donor squaramide [20] revealed that it had al arge influence on the enantioselectivity,w ith catalysts 5a-c affording significantly improved enantioselectivities (entries [4][5][6]. However,v ariation of the thiourea moiety of the catalyst with more acidic double hydrogen-bond donor squaramide [20] revealed that it had al arge influence on the enantioselectivity,w ith catalysts 5a-c affording significantly improved enantioselectivities (entries [4][5][6].…”

“…[5] The prominentelemento ft hese challenges is the stereoselectivec onstruction of quaternary carbon stereocenters, [6] of which terpenoidsa re richly endowed. [5] The prominentelemento ft hese challenges is the stereoselectivec onstruction of quaternary carbon stereocenters, [6] of which terpenoidsa re richly endowed.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…Specific compounds or compound classes represented include: (1) tetrahydropyrans [53]; (2) cyclopentenones [54]; (3) 3,4,5-trisubstituted isoxazolines [55]; (4) carbocyclic nucleosides [56]; (5) lycopodium alkaloids [57,58]; (6) cyclic hydrazines and azo compounds [59]; (7) tropone and tropolone natural products [60]; (8) seven-membered ring natural products [61]; [62]; (9) tetrahydroisoquinoline-3-carboxylic acid derivatives [63]; (10) chalcones and their heterocyclic derivatives [64]; (11) marine-derived cyclic ethers [65]; (12) pericosine and related marinederived carbasugar natural products [66]; (13) carbohydrate derived macrocyclic compounds [67]; (14) neurotrophic natural products [68]; (15) isodon diterpenes [69]; (16) non-isoprenoid polyene natural products [70]; (17) heterophosphacyclanes [71]; (18) chlorosulfolipids [72]; (19) seven-membered ring sulfur heterocycles; (20) organic cage compounds [73]; (21) presilphiperfolanols [74]; (22) pleuromutilin [75]; (23) hyperforin [76]; (24)…”

Two New Sesquiterpene Alcohols Isolated from Senecio hadiensis Forssk. Grown in Saudi Arabia

“…The presilphiperfolanols are biosynthetic precursors to many polycyclic sesquiterpenes, some have pleasant olfactory properties and it was reported to possess insect antifeedant and antimycobacterial activities …”