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.     

First total synthesis of parvistone C and its C8-epimer

Diastereoselective first total synthesis of parvistone C 1 and C8-epimer 1a are described. The key features of our synthesis include Sharpless asymmetric dihydroxylation, stereoselective aryl Grignard reactions, Still–Gennari olefination, and intramolecular cyclization.     

Stereoflexible total synthesis of (−)-epiquinamide

Hydroxy propiolate rearrangement to conjugated diene, Sharpless asymmetric dihydroxylation and one-pot quinolizine construction have been used as key steps in the total synthesis of (−)-epiquinamide.     

An efficient total synthesis of (+)-Cladospolide C

The asymmetric synthesis of (+)-Cladospolide C has been achieved in 11 steps with 26% overall yield. Key steps in the sequence involve KAPA-promoted alkyne Zipper reaction, TPP-promoted enyne ester (ynoate) to diene ester (dienoate) isomerization, Sharpless asymmetric dihydroxylation and Yamaguchi macrolactonization.     

Formal total synthesis of borrelidin: synthesis of C1-C11 fragment via desymmetrization strategy

A stereoselective formal total synthesis of borrelidin is described. The synthetic strategy for synthesis of C1-C11 fragment features desymmetrization of Diels-Alder adduct, Sharpless asymmetric epoxidation, regioselective opening of chiral epoxide, and alkylation using Evans chiral auxiliary.     

Asymmetric synthesis of (+)-tetrahydropseudodistomin

An efficient asymmetric synthesis of (+)-tetrahydropseudodistomin is described. The important synthetic features include a Maruoka asymmetric allylation and a Sharpless asymmetric dihydroxylation as key steps for the generation of chirality at C-2, -4, and -5 of the trisubstituted piperidine ring.     

A practical total synthesis of (+)-isogalbulin and (+)-galbulin

A practical total synthesis of the natural products (+)-isogalbulin and (+)-galbulin has been achieved in 10 steps from readily available 3-(3,4-dimethoxyphenyl)propanoic acid. The total yields were 12.3% and 12.9%, respectively. The key steps involved Evans asymmetric alkylation, Sharpless asymmetric epoxidation, and a highly regioselective opening of 1-benzyloxy-2,3-epoxides with an organoaluminum ate-complex formed by Me₃Al and n-BuLi.     

A highly stereocontrolled asymmetric total synthesis of epimer of (+)-7-deoxypancratistatin

A highly stereocontrolled asymmetric total synthesis of epimer of (+)-7-deoxypancratistatin has been achieved from readily available starting materials via unified strategy employing Sharpless asymmetric dihydroxylation, ring closing metathesis, Overman rearrangement, hydrogenolysis and Bischler–Napieralski reaction in 15 purification steps with 15% overall yield.     

Total synthesis of the proposed structure of xylarolide

A total synthesis of a proposed structure of xylarolide is described. The key features of the synthesis include Sharpless asymmetric reaction, Wittig olefination, Sharpless asymmetric dihydroxylation, Still-Gennari olefination and Yamaguchi lactonization. The differences in the spectroscopic data of the synthetic and natural product indicate a revision of the assigned structure.     

Stereoselective total synthesis of (+)-anamarine via cross-metathesis protocol

A convergent stereoselective total synthesis of (+)-anamarine via cross-metathesis (CM) protocol starting from 2-butyn-1,4-diol and vinyl lactone is reported. Other key features of the strategy include the use of Sharpless asymmetric epoxidation, Sharpless dihydroxylation, and Red-Al reduction.     

An efficient approach for the total synthesis of balticolid

An efficient stereoselective total synthesis of balticolid has been accomplished starting from known aldehyde. The key steps involved in this synthesis are Sharpless asymmetric epoxidation, Wittig olefination, alkylation of 1,3-dithiane and Yamaguchi macrolactonization.     

Asymmetric total synthesis of phomonol

An efficient asymmetric total synthesis of phomonol 1 is presented, starting from (S)-1,2-epoxypentane. The synthesis features Sharpless asymmetric dihydroxylation (AD), diastereoselective reductive etherification and Wacker oxidation as key steps.     

First stereoselective total synthesis of decytospolides A and B

The first stereoselective total synthesis of decytospolides A and B has been accomplished starting from n-hexanal. The key steps involved in this synthesis are Horner-Wittig reaction, Sharpless asymmetric epoxidation, and oxa-Michael reaction.     

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 oplopandiol,oploxyne A,and oploxyne B

A stereoselective total synthesis of oplopandiol, oploxyne A, and (−)-oploxyne B is described. The key reactions include Sharpless asymmetric epoxidation, d-proline catalyzed aminoxylation, Cadiot–Chodkiewicz cross-coupling reaction, m-CPBA induced substrate-controlled stereoselective epoxidation, and Lewis acid catalyzed stereo- and regioselective ring-opening of epoxide.     

Stereoselective Synthesis of Tetrahydropyran D-Ring of Methyl Sartortuoate

A stereoselective synthesis of functionalized tetrahydropyran D‐ring of methyl sartortuoate ( 1 ) was achieved starting from geraniol in a high yield. Sharpless asymmetric kinetic resolution, asymmetric dihydroxylation as well as asymmetric epoxidation were applied as key steps to establish all the four stereocenters of the D‐ring.     

Formal total synthesis of (−)-spongidepsin

The formal total synthesis of (−)-spongidepsin is described. Three fragments I, II, and III were first prepared from readily available starting materials and then assembled to the target compound. The key steps involved in the synthesis are asymmetric α-hydroxylation, Ender's alkylation, and ring-closing metathesis reactions. An alternative route for the fragment II is also achieved involving Sharpless asymmetric epoxidation and Gilman's alkylation as key reactions.     

Efficient total synthesis of iso-cladospolide B and cladospolide B

An efficient synthesis of iso-cladospolide B and cladospolide B has been achieved using Jacobsen’s hydrolytic kinetic resolution (HKR), Sharpless asymmetric dihydroxylation and Yamaguchi macrolactonization as the key steps.     

A concise and stereoselective synthesis of (+)- and (−)-deoxoprosophylline

An efficient synthesis of (+)- and (−)-deoxoprosophylline was accomplished from the readily available cis-2-butene-1,4-diol in which the Sharpless asymmetric dihydroxylation was used as the key step.     

Asymmetric Synthesis of Chiral Flavan-3-Ols

Flavan-3-ols are a series of natural products widely present in plants and show versatile biological activities. The structures of such compounds are characterized by owing two adjacent chiral centers and three rings. Their interesting structures and promising biological activities have driven increasing research developments toward the preparation of enantioenriched flavan-3-ols. This review summarizes the recent approaches for the asymmetric synthesis of chiral flavan-3-ols from two strategies in the construction of chiral centers. The key steps in the synthetic protocol involve Sharpless asymmetric dihydroxylation, Shi asymmetric epoxidation and Sharpless asymmetric epoxidation.