The first enantioselective total synthesis of penostatin E has been accomplished. Two highly efficient and diastereoselective reactions, a Hosomi–Sakurai allylation and an intramolecular Pauson–Khand reaction, were utilized for the construction of the basic carbon framework of the target molecule as the key steps. A late-stage introduction of the side chain and a successful base-promoted elimination reaction afforded an efficient synthetic route to (+)-penostatin E.

The first enantioselective total syntheses of pygmaeocins B and C have been accomplished using an efficient and highly diastereoselective intramolecular Heck cyclization for the construction of a quaternary stereogenic center and the functionalized A-ring of the natural products as the key step.

A novel and highly diastereoselective intramolecular carbamoylketene/alkene [2 + 2] cycloaddition has been developed, and the methodology was successfully applied to the enantioselective syntheses of (−)-esermethole and Takayama’s intermediate for (+)-psychotrimine.

Total syntheses of the dimeric pyrrolidinoindoline alkaloids folicanthine and chimonanthine have been accomplished in racemic forms employing a double intramolecular carbamoylketene–alkene [2+2] cycloaddition as the key step.

The first total synthesis of penostatin B has been accomplished by using a highly diastereoselective Pauson–Khand reaction and an efficient relay ring-closing metathesis for the construction of the basic carbon skeleton of the natural product as the key steps.

The enantiocontrolled total syntheses of three ionone type bisnorsesquiterpenes have been accomplished employing a highly diastereoselective intramolecular Heck reaction as the key step.

The first enantiocontrolled total synthesis of heliespirone B has been accomplished employing a biomimetic intramolecular oxy-Michael reaction followed by the regio- and diastereoselective reduction of the carbonyl function as key steps.

A full account of the development of a novel type of the intramolecular Hosomi-Sakurai reactions of the substrates with a p-benzoquinone and an allylsilane moieties connected by an ether linkage is described. This transformation proceeds via an addition–elimination sequence and provides the products with two stereogenic centers through a 1,3(or 1,4)-asymmetric induction in good to excellent diastereoselectivities. A reasonable mechanistic possibility for the reaction, determination of the stereochemistry for the product, and scope and limitation of the transformation are also discussed. The methodology developed here can successfully be applied to the enantiocontrolled total synthesis of the natural enantiomers of (−)-heliespirone A and (+)-heliespirone C, which have been isolated from sunflower Helianthus annuus L. as allelochemicals.

Total synthesis of debromoflustramines B and E has been accomplished by using a platinum-catalyzed addition reaction of o-aminophenylboronic acid with the allene and an intramolecular carbamoylketene–alkene [2 + 2] cycloaddition for the construction of the basic carbon framework of the target alkaloids as the key steps.

Enantiocontrolled total syntheses of the breviones A, B, and C have been accomplished using a highly diastereoselective oxidative coupling of an α-pyrone with a tricyclic diene prepared from an optically pure Wieland–Miescher ketone derivative through the 7-endo-trig mode of acyl radical cyclization.

The second-generation enantioselective total synthesis of aspergillide C, a new type of 14-membered macrolide isolated from a marine-derived fungus, has been accomplished in a longest linear sequence of 15 steps from a chiral building block in 19% overall yield employing the 6-exo-trig transannular oxy-Michael reaction as the key step.

The enantioselective total synthesis of aspergillide C, a member of a novel class of 14-membered macrolides isolated from the marine-derived fungus Aspergillus ostianus strain 01F313, has been accomplished employing a highly diastereoselective intramolecular oxy-Michael reaction as the key step.

The first enantioselective total synthesis of aspermytin A, a new neurotrophic polyketide isolated from a cultured marine fungus of the genus Aspergillus sp., has been accomplished in 24 steps with an overall yield of 9.7% from S-(−)-citronellal.

A general and enantiocontrolled synthetic route to 2-arylpropionic acids, represented by non-steroidal anti-inflammatory drugs S-naproxen 1a and S-ibuprofen 1b, has been developed by employing the lipase-mediated asymmetric acetylation of prochiral 2-aryl-1,3-propanediol 3, which has been derived via a Heck reaction, as the key step.Graphic

The second-generation enantioselective total synthesis of aspergillide C, a new type of 14-membered macrolide isolated from a marine-derived fungus, has been accomplished in a longest linear sequence of 15 steps from a chiral building block in 19% overall yield employing the 6-exo-trig transannular oxy-Michael reaction as the key step.