Catalytic asymmetric allylation of aldehydes via a chiral indium(iii) complex

Abstract

A chiral indium complex has been discovered to effect high enantioselectivities in the addition of allyltributyl stannanes to aldehydes. The allylation of a variety of aromatic, alpha,beta-unsaturated and aliphatic aldehydes resulted in good yields and high enantioselectivities (90-96% ee).

The Future of Main Group Chemistry

“…[131] A water-tolerant chiral In(III) catalyst has also been developed and shows promise in enantioselective reactions. [132] The addition of hydrogen to unsaturated organic compounds (hydrogenation) is used extensively in industry in transformations as diverse as the processing of oils and the production of chemicals for use in the agricultural and pharmaceutical industries. These processes are usually mediated either by homogeneous or heterogeneous transition-metalbased catalysts.…”

Formal Synthesis of Natural 1,3‐Polyol/α‐Pyrone Diastereoisomers

“…Acetonide protection of the diol followed by DIBAL-H reduction gave aldehyde 13. We envisioned that a chiral asymmetric allylation [8] of aldehyde 13 could be achieved using allyltributylstannane and a chiral Lewis acid. Thus treatment of aldehyde 13 with allyl(tributyl)stannane and (R)-BINOL afforded the chiral homoallyl alcohol 14 in good yield with high enantioselectivity.…”

Application of Tandem Ring-Closing Enyne Metathesis: Formal Total Synthesis of (−)-Cochleamycin A

“…Asymmetric allylation utilizing the pseudoephedrine derived strained silacycle 9 developed by Leighton and coworkers, afforded homoallylic alcohol 10 in 74% yield and 77% enantiomeric excess (ee) 17. Many other conventional aymmetric allylation protocols including Brown’s allylation,18 Roush allylation,19 Keck allylation,20 or Loh’s indium mediated allylation21 failed to provide acceptable yields or enatiomeric excess. We suppose, this should be caused by possible chelation of the dithiane moiety to the allylating agents disabling the complexation of the aldehyde.…”