Diphenylprolinol silyl ether was found to catalyze the formal carbo [3 + 3] cycloaddition reaction through the domino reaction via the Michael reaction, followed by Knoevenagel condensation of the alpha,beta-unsaturated aldehyde and dimethyl 3-oxopentanedioate, affording substituted cyclohexenone derivatives with excellent enantioselectivity.

Remote stereocontrol is a difficult topic in current organic synthesis. We have developed a highly diastereoselective 1,4-asymmetric induction using a cobalt alkyne complex. This is the first example of using a cobalt alkyne complex for a stereoselective reaction via 1,4-chelation. Both anti and syn isomers were stereoselectively synthesized using two different methods.

L‐Proline‐mediated α‐aminoxylation is a key step in the enantio‐ and diastereoselective total syntheses of fumagillin, ovalicin, and related compounds (see scheme). These compounds contain a cyclohexane ring, two epoxides, and five or six contiguous stereogenic centers, and they display anti‐angiogenesis or immunosuppressive properties.

The synthesis of a protected dephosphofostriecin, and thereby a formal synthesis of fostriecin, has been accomplished. Two of the four chiral centers are controlled by an external chiral auxiliary and the other two are synthesized stereoselectively, one by a novel 1,4-asymmetric induction using cobalt-alkyne complex, and the other by 1,3-asymmetric induction.

The synthesis of a protected dephosphofostriecin, and thereby a formal synthesis of fostriecin, has been accomplished. The synthetic challenges were the construction of four stereogenic centers and the conformationally labile cis-cis-trans-triene moiety. Previous total syntheses have employed at least two asymmetric reactions that required the use of an external chiral auxiliary. Although remote stereoinduction in a 1,4-relationship is considered difficult, we have developed a notable 1,4-asymmetric induction that utilizes an alkyne-cobalt complex for the control of C5 stereochemistry by the C8 stereogenic center. The stereochemistry at C11 was established by 1,3-asymmetric induction with a higher-order alkynyl-zinc reagent. Thus, only one asymmetric reaction requiring an external chiral auxiliary was employed in this route. The labile cis-cis-trans-triene unit was constructed at a late stage of the synthesis by diastereoselective coupling of a dienyne and an aldehyde unit, followed by reduction.