Recent development on the [5+2] cycloadditions and their application in natural product synthesis
The recent developments on the [5+2] cycloadditions and their application in the synthesis of complex natural products are discussed.
Regioselective side-chain amination of 2-alkyl azacycles by radical translocation: total synthesis of tetraponerine T8
Radical translocation facilitates the regioselective γ-amination of 2-alkyl-substituted azacycles, leading to 1,3-diamines including the alkaloidal natural product tetraponerine T8.
Access to 1-indolyltetrahydro-β-carbolines via metal-free cross-dehydrogenative coupling: the total synthesis of eudistomin U, isoeudistomin U and 19-bromoisoeudistomin U
A highly selective metal-free CDC approach for the synthesis of 1-indolyltetrahydro-β-carbolines is developed. The total synthesis of biologically important alkaloids, eudistomin U and isoeudistomin U and the first total synthesis of 19-bromoisoeudistomin U were accomplished.
Collective enantioselective total synthesis of (+)-sinensilactam A, (+)-lingzhilactone B and (−)-lingzhiol: divergent reactivity of styrene
The collective total synthesis of (+)-sinensilactam A, (+)-lingzhilactone B, (+)-lingzhilactone C and (−)-lingzhiol has been accomplished from a common epoxide intermediate 9.
A macrocycle directed total synthesis of di-O-methylendiandrin A
The synthesis of di-O-methylendiandrin A has been achieved using diastereoselective, vicinal alkylation and transannular McMurry reactions of a macrocyclic 1,4-diketone, to establish stereochemistry and the strained ring of the natural product.
Chemoenzymatic, biomimetic total synthesis of (−)-rugulosin B, C and rugulin analogues and their biosynthetic implications
Flavoskyrins, (−)-rugulosin B, C and rugulin analogues are synthesized chemoenzymatically from anthraquinones in two, three and four steps, respectively.
Total synthesis and biological evaluation of simplified aplyronine analogues as synthetically tractable anticancer agents
Analysis of bound structures and SAR studies led to the function-oriented simplification of the aplyronines; a convergent and modular synthetic platform then enabled the total synthesis and biological evaluation of four novel analogues.
Exploration of a KI-catalyzed oxidation system for direct construction of bispyrrolidino[2,3-b]indolines and the total synthesis of (+)-WIN 64821
A facile and environmentally benign KI(cat.)/NaBO3·4H2O oxidation system has been developed for the tandem oxidative aminocyclization/coupling of tryptamines, affording a series of 3a,3a′-bispyrrolidino[2,3-b]indolines with high efficiency (up to 94% yield).
Total synthesis of verucopeptin, an inhibitor of hypoxia-inducible factor 1 (HIF-1)
The first total synthesis of vercopeptin (1), an inhibitor of hypoxia-inducible factor 1 (HIF-1), was achieved via condensation of the depsipeptide core and the polyketide side chain unit.
Total synthesis and antimalarial activity of mortiamides A–D
This work describes the first total synthesis of mortiamides and their anti-malarial activity against a multi-drug resistant strain of Plasmodium falciparum.
Organocatalytic enantioselective direct alkylation of phloroglucinol derivatives: asymmetric total synthesis of (+)-aflatoxin B2
The organocatalytic enantioselective Friedel–Crafts alkylation of the phloroglucinol derivatives with enals is reported, providing general access to the benzylic chiral centers shown in a variety of phloroglucinol natural products.
A synthetic approach to chrysophaentin F
A synthetic approach to chrysophaentin F is described featuring an array of metal catalysed coupling reactions (Cu, Ni, Pd, W, Mo).
Divergent total syntheses of five illudalane sesquiterpenes and assignment of the absolute configuration
Transition metal catalyzed [2+2+2] cycloaddition and aromatic C–H oxygenation enables concise, divergent total syntheses of five bioactive illudalane sesquiterpenes.
First total synthesis of ent-asperparaline C and assignment of the absolute configuration of asperparaline C
The first asymmetric total synthesis of a member of the asperparaline family was accomplished and the unknown absolute configuration of asperparaline C has been determined to be all-(S).
Unified enantioselective total syntheses of (−)-scholarisine G, (+)-melodinine E, (−)-leuconoxine and (−)-mersicarpine
A unified strategy enabled the enantioselective syntheses of (−)-scholarisine G, (+)-melodinine E, (−)-leuconoxine and (−)-mersicarpine from a common 2-alkylated indole bearing an all-carbon quaternary stereogenic center.
A concise synthesis and biological study of evodiamine and its analogues
Efficient access to evodiamine and its analogues is presented via Lewis acid catalysis. In this reaction, three chemical bonds and two heterocyclic-fused rings are constructed in one step.
A desymmetrization-based approach to morphinans: application in the total synthesis of oxycodone
Here we report a total synthesis of the pharmacologically significant morphinan alkaloid, oxycodone.
Catalytic stereoselective total synthesis of a spiro-oxindole alkaloid and the pentacyclic core of tryptoquivalines
An expedient route to the pentacyclic core of the tryptoquivaline alkaloids and the total synthesis of natural product (+)-3′-(4-oxoquinazolin-3-yl)spiro[1H-indole-3,5′-oxolane]-2,2′-dione (1) have been achieved.
Asymmetric total synthesis of pleurospiroketals A and B
The first asymmetric total synthesis of pleurospiroketals A and B has been accomplished in 16 steps from 5-methyl-5-hexenoic acid.
Total synthesis of (−)-agelastatin A: an SH2′ radical azidation strategy
A new synthetic approach to (−)-agelastatin A has been established through the strategic implementation of brominative olefin transposition of a silyl enol ether and subsequent SH2′ radical azidation of the resultant allylic bromide.
Asymmetric total synthesis of (+)-ovafolinins A and B
Benefiting from a highly diastereoselective alkylation of (S)-Taniguchi lactone, a double Friedel–Crafts reaction, a global debenzylation and a Cu(OAc)2-enabled benzylic oxidative cyclization, an efficient synthetic approach to (+)-ovafolinins A and B has been developed.
Enantioselective total synthesis of sagittacin E and related natural products
The first enantioselective total synthesis of eremophilane-type sesquiterpenoids, sagittacin E and related natural products, was achieved.
Alkene protection against acid using a bromide substituent: application in a total synthesis of (−)-6,7-dideoxysqualestatin H5
Alkenyl bromide functionality survives several synthetic steps, including an acid-induced rearrangement, before a stereoretentive methylative debromination gives the natural product.
A divergent and concise total synthesis of (−)-lycoposerramine R and (+)-lycopladine A
A concise, asymmetric and divergent synthesis of lycoposerramine R and lycopladine A is presented.
Nine-step total synthesis of (−)-strychnofoline
The asymmetric synthesis of an anti-cancer spirooxindole alkaloid, (−)-strychnofoline, has, for the first time, been accomplished in only nine steps.
Total synthesis of conosilane A via a site-selective C–H functionalization strategy
The strategy developed for the first total synthesis of highly oxygenated natural product conosilane A involving double manipulation of allylic C(sp3)–H functionalization renders the power of C–H functionalization in organic syntheses.
Catalytic asymmetric formal total syntheses of (+)- and (−)-cycloclavine
Catalytic asymmetric formal syntheses of both enantiomers of (+)- and (−)-cycloclavine (1) have been envisioned via proline catalysed α-aminoxylation of aldehydes followed by an intramolecular Heck cyclization to set vicinal stereocenters.
Total synthesis of (+)-brasilenyne via concise construction of an oxonane framework containing a 1,3-cis,cis-diene
The enantioselective total synthesis of (+)-brasilenyne, which has a unique oxonane framework containing a 1,3-cis,cis-diene, has been accomplished.
About this collection
Collated by Antonio Echavarren (ICIQ, Spain), this collection showcases syntheses designed as a proof of the applicability of a new synthetic methods as well as for the obvious purpose of accessing to biologically relevant molecules, although in occasions these synthesis still fulfill the traditional objective of definitively assigning the structure of the natural product.