Stereoselective total synthesis of cytotoxic sporiolide A

A simple and highly efficient stereoselective total synthesis of cytotoxic agent sporiolide A has been achieved starting from d-mannitol; the strategy of synthesis utilizes stereoselective zinc-mediated allylation, aldol coupling and ring-closing metathesis as key steps.     

First total synthesis of herbarumin III

An asymmetric 10-step total synthesis of herbarumin III in 24% overall yield is described using ring-closing metathesis as the key step.     

Total synthesis of Z-isomer of phomolide B

We have achieved the synthesis of Z-isomer of phomolide B during our investigation toward the effect of protecting group on the outcome of ring-closing metathesis reaction. The other key reactions involved are cis-selective partial hydrogenation, Sharpless asymmetric epoxidation, Yamaguchi esterification, and following 12 longest linear sequence with 18.5% overall yield starting from a known intermediate 20.     

Total synthesis of proposed structure of xylogiblactone B by chiron approach

Total synthesis of the proposed structure of xylogiblactone B is described using d-(+)-mannitol, regioselective epoxide ring-opening, Yamaguchi esterification, and ring-closing metathesis as key steps.     

Stereoselective total synthesis of polyrhacitide A

Stereoselective total synthesis of polyketide lactone isolated from Chinese medicinal ant Polyrhacis lamellidens is described. Ring-closing metathesis followed by stereoselective intramolecular oxa-Michael addition reactions were used to construct the bicyclic lactone moiety in the molecule and l-malic acid was used as a chiral pool material     

Enantioselective synthesis of decarestrictine J

An efficient total synthesis of decarestrictine J has been achieved using ring-closing metathesis and Yamaguchi esterification as key steps. The stereogenic centres were generated by means of iterative hydrolytic kinetic resolution (HKR) of racemic epoxides.     

The stereoselective total synthesis of PF1163A

A stereoselective total synthesis of 13-membered macrocycle PF1163A, an antifungal agent, has been accomplished for the first time starting from d-xylose. This approach involves a diastereoselective allylation of lactal ether,^3a reductive ring opening of tetrahydrofuran ring,^3b asymmetric methylation reaction, Yamaguchi esterification, and ring closing metathesis as key steps.     

The first total synthesis of (±)-laurokamurene B

The first total synthesis of the rearranged aromatic sesquiterpene (±)-laurokamurene B, isolated from the Chinese red alga Laurencia okamurai Yamada, has been accomplished, confirming the structure of the natural product. A combination of Ireland-Claisen rearrangement and ring-closing metathesis was employed as key reactions.     

The first stereoselective synthesis of dendrodolide A

The first stereoselective total synthesis of natural product, dendrodolide A (1) is described from readily available (R)-propylene oxide and 3-buten-1-ol as starting materials. The synthesis was achieved in 10 steps with an overall yield of 19.1%. The key steps involved in the synthesis are Jacobsen hydrolytic kinetic resolution, epoxide ring opening with 2-allyl-1, 3-dithiane, Yamaguchi esterification, and ring-closing metathesis (RCM).     

Stereoselective total synthesis of xyolide

A stereoselective total synthesis of xyolide is described employing MacMillan α-hydroxylation, Steglich esterification, and ring closing metathesis as key steps. The use of organocatalytic MacMillan α-hydroxylation to construct two of the chiral centers of the xyolide makes this approach attractive.     

Total synthesis of the proposed structure of iriomoteolide-1a

Full details of the total synthesis of the proposed structure of iriomoteolide-1a (1) are described. The key steps include (i) a Sakurai reaction between allylsilane 11 and aldehyde 10 that bears both a tertiary chiral center and vinyl iodide moiety (ii) an anti-aldol reaction to construct the C18/C19 chiral centers (iii) a B-alkyl Suzuki-Miyaura coupling reaction to assemble the C7-C23 fragment, and (iv) a macrocyclic ring-closing metathesis to complete the construction of the target molecule. Two different approaches to access penultimate precursor 2 are delineated. The NMR spectra of the synthetic iriomoteolide-1a (1) were found not to match those reported for the natural product bringing into question its true structural identity.     

Stereoselective total synthesis of 10-epi-tirandamycin E

A stereoselective total synthesis of 10-epi-tirandamycin E is described, employing desymmetrization protocol, ring-closing metathesis (RCM), acid-catalyzed ketalization, substrate controlled dihydroxylation and Horner-Wadsworth-Emmons olefination as key reactions.     

The first total synthesis of sporiolide B

The first total synthesis of natural cytotoxic agent, sporiolide B, is described. d-Xylose was used as the chiral template to pre-control the absolute configuration during the synthesis. Yamaguchi esterification and ring closing metathesis greatly facilitate the target compound accomplishment.     

Stereoselective synthesis of the cytotoxic macrolide aspergillide B

A total, stereoselective synthesis of the cytotoxic macrolide aspergillide B has been performed. A cross metathesis and a C-glycosidation via a Mukaiyama-type aldol reaction were key features of the synthesis. The macrocyclic lactone ring was created by means of the Yamaguchi procedure.     

Stereoselective synthesis of (+)-lauthisan

Stereoselective synthesis of (+)-lauthisan has been accomplished starting from d-glyceraldehyde acetonide by combination of diastereoselective alkylation and ring-closing metathesis. High degree of 1,3-asymmetric induction has been realized in ether system.     

First asymmetric total synthesis of aspinolide A

The first total synthesis of aspinolide A has been achieved using ring-closing metathesis as a key step. The stereogenic centers were generated by means of hydrolytic kinetic resolution (HKR) of racemic epoxides.     

Stereoselective synthesis of anamarine

A stereoselective synthesis of the naturally occurring, α,β-unsaturated lactone anamarine is described. The key step was a highly stereoselective aldol reaction of a protected erythrulose derivative with a chiral aldehyde. Another relevant step was an asymmetric aldehyde allylation with a chiral allylborane. The lactone ring was made by means of a ring-closing metathesis.     

Stereoselective synthesis of cryptomoscatone D2

Cryptomoscatone D2 was synthesized stereoselectively from trans-cinnamaldehyde. The synthesis of the triol frame work relied on the creations of the stereocenters independently by utilizing double Maruoka allylations and Sharpless epoxidation. The lactone moiety was constructed by RCM reaction.     

Stereoselective synthesis of the cyclic ether core of (+)-laurenyne

A concise enantioselective synthesis of the cyclic ether core of the marine natural product (+)-laurenyne has been accomplished using ring-closing metathesis for medium-ring construction.     

Total synthesis of the tricyclic humulanolide wilfolide B

The first total synthesis of tricyclic humulanolide wilfolide B was achieved. The synthetic strategy involved: i) radical cyclization with samarium(II) iodide to construct the bicyclic lactone from an acyclic compound, and ii) ring-closing metathesis to build the eight-membered ring by connecting two side chains, thus completing the tricyclic framework.