First stereoselective total synthesis of triumfettamide

The first total synthesis of triumfettamide (1) is described. The asymmetric syntheses of two highly functionalized units—α-hydroxylated C17 monounsaturated fatty acid unit (2) and C26 phytosphingosine (3) have been accomplished involving Sharpless asymmetric dihydroxylation, Sharpless kinetic resolution, regioselective epoxide opening, regioselective DIBAL-H reduction of acetal, Wittig olefination as the key steps. Finally N-acylation of phytosphingosine 3 with (2R,6Z)-2-hydroxy-6-heptadecenoic acid 2 followed by DDQ deprotection of PMB, provided target compound 1.     

First stereoselective total synthesis of Phomolide G and H via RCM protocol

A first total synthetic route has been reported for the synthesis of Phomolide G and H. The syntheses of fragments were initiated from commercially available and inexpensive starting material (R)-epichlorohydrin. The synthesis involves a key Sharpless epoxidation, stereoselective epoxide opening, lactonization and ring closing metathesis (RCM).     

First stereoselective total synthesis of trichodermone A

The first stereoselective total synthesis of trichodermone A using Baylis-Hillman and ring-closing metathesis (RCM) reactions as key steps is reported.     

First stereoselective total synthesis of panaxjapyne C

The first stereoselective total synthesis of polyacetylene panaxjapyne C is described. The key reactions include regioselective opening of the epoxide and Cadiot-Chodkiewicz cross-coupling reactions. l-Ascorbic acid was used as a chiral pool material for the construction of the both terminal acetylenes.     

First stereoselective total synthesis of pectinolide H

The stereoselective total synthesis of bio-active pectinolide H (1) is described. Midland’s asymmetric reduction, Sharpless dihydroxylation reactions are involved in generating the stereogenic centers at C-4′, C-5 and C-1′. Other key steps in the synthesis are Sonogashira cross coupling, Z-selective Still–Gennari olefination, one-pot acetonide deprotection–lactonization, and Lindlar’s reaction. This offers a distinctive strategy for the synthesis of γ-lactones.     

First stereoselective total synthesis of Goniothalesdiol A

The first total synthesis of Goniothalesdiol A, isolated from the stems of Goniothalamus amuyon (Annonaceae) is reported. The C2 stereocentre and C3/C4 syn diol were created by a Sharpless kinetic resolution followed by acetonide formation. The tetrahydropyran ring was formed and the C6 stereocentre was fixed by intramolecular oxy-Michael addition.     

First stereoselective total synthesis of (+)-dodoneine

The first stereoselective total synthesis of the natural product (+)-dodoneine is described involving a Crimmins aldol reaction and a Horner-Wadsworth-Emmons olefination as the key steps.     

First stereoselective total synthesis of pectinolide A

The enantioselective synthesis of bio-active 5,6-dihydro-α-pyrone, pectinolide A, has been achieved in 10 steps in good overall yield. Of the three stereogenic centres, the C-5/C-6 vic-diol was obtained using diastereo- and enantioselective Brown hydroxyl crotylation, while the C-3′ stereocentre was created by Jacobsen hydrolytic kinetic resolution method.     

First stereoselective total synthesis of seimatopolide A

The first stereoselective total synthesis of seimatopolide A (1) has been achieved. The key steps are Keck allylation, Sharpless asymmetric dihydroxylation, cross-, and ring-closing metathesis reactions.     

Stereoselective total synthesis of stagonolide E

The first total synthesis of a 10-membered macrolide, stagonolide E is described from readily available 4-penten-1-ol. The synthetic strategy involves Jacobsen’s kinetic resolution, Sharpless epoxidation, Stille-Gennari, and Yamaguchi lactonization as key reactions.     

First stereoselective total synthesis of decytospolides A and B

The first synthesis of bioactive decytospolides A and B adopting an oxa-Michael addition as the key step is reported.     

First stereoselective total synthesis of helicascolides A and C

The first total synthesis of helicascolides A and C is reported via acid catalyzed acetonide deprotection followed by intramolecular lactonization in one-pot as the key step.     

First stereoselective total synthesis of antibiotic macrolide Berkeleylactone F

The first stereoselective total synthesis of antibiotic macrolide Berkeleylactone F is described. The synthetic sequence notably features Sharpless kinetic resolution to access chiral epoxide followed by its regioselective ring-opening reaction, Sharpless asymmetric reaction and ring-closing metathesis.     

The total synthesis and structural revision of stagonolide D

The total synthesis of the putative structure of stagonolide D has been completed. The relative and absolute configuration of stagonolide D was established by synthesizing its optical antipode. The adopted strategy involves the construction of the central macrolide employing ring-closing metathesis (RCM), followed by selective protecting group manipulations and a final concomitant -OTBS deprotection and displacement of an -OMs placed next to it, resulting in the formation of the epoxide ring.     

Stereoselective synthesis of revised structure of stagonolide G

A concise total synthesis of the revised structure of stagonolide G has been achieved in 11 steps and with an overall yield of 31.7%. Key reaction sequence includes BAIB/TEMPO mediated tandem oxidation and lactonization, Lindlar’s hydrogenation, regioselective epoxide opening by an in situ generated alkynyl as nucleophile, Sharpless asymmetric dihydroxylation, and Jacobsen kinetic resolution.     

First stereoselective total synthesis of decarestrictine O via RCM protocol

A convergent first stereoselective total synthesis of decarestrictine O via RCM protocol starting from 1,3-propanediol and propylene oxide is reported.     

First stereoselective total synthesis of Neocosmosin A: a facile approach

First stereoselective concise synthesis of Neocosmosin A, with in vitro binding affinity for human opioid and cannabinoid receptors, has been reported using readily available starting materials such as methylacetoacetate, cyclohexanone, and homoallyl alcohol involved in the key transformations. There are three fragments involved in the synthesis of target molecule, bearing acid functionality, (R)-pent-4-en-2-ol, and Weinreb amide which are synthesized in four, eight, and three steps, respectively. Then the fragments were coupled in four steps to yield the target molecule in an overall yield of 28.6%.     

Total synthesis of stagonolide B

Asymmetric total synthesis of nonenolide stagonolide-B has been presented in this Letter. The main highlight of our synthetic strategy is the application of hydroxynitrile lyase (ParsHNL) mediated asymmetric synthesis of cyanohydrin, Sharpless asymmetric dihydroxylation, cross metathesis (CM) reaction, stereoselective Keck allylation reaction and Yamaguchi macrolactonization at a late stage enables us to achieve the synthesis of the target molecule in an efficient way.     

First total synthesis of salinipyrone A using highly stereoselective vinylogous Mukaiyama aldol reaction

A synthetic approach for the total synthesis of salinipyrone A has been developed. Key steps involve the TiCl₄-mediated vinylogous Mukaiyama aldol reaction (VMAR) of chiral ketene silyl N,O-acetal with propionaldyhyde, an aldol condensation, Witting olefination, and a cyclization. The synthesis proceeds in eight steps.     

The stereoselective total synthesis of isocladosorpin

A highly stereoselective total synthesis of isocladosorpin is described. The key steps involved in this synthesis are oxa-Michael reaction, asymmetric propargylation, and Alder–Rickerts reaction.