Stereocontrol in intramolecular hydrosilylation of allyl and homoallyl alcohols: a new approach to the stereoselective synthesis of 1,3-diol skeletons

Stereoselective Synthesis of syn,syn- and syn,anti-1,3,5-Triols via Intramolecular Hydrosilylation of Substituted Pent-3-en-1,5-diols

“…Intramolecular hydrosilylation of acyclic homoallylic alcohols followed by oxidative cleavage of the resultant carbon-silicon bond presents a mild and efficient way to construct 1,3-diols 5-7. Several publications by the Tamao group described the regio- and stereocontrolled synthesis of 1,3-diols from allylic and homoallylic alcohols 5,6a.…”

“…Several publications by the Tamao group described the regio- and stereocontrolled synthesis of 1,3-diols from allylic and homoallylic alcohols 5,6a. However, 1,3-stereochemical control was not observed in hydrosilylation reactions of acyclic ( E) - and ( Z) - disubstituted homoallylic alcohols by using Speier’s catalyst (H 2 PtCl 6 •6H 2 O) 5,8. Further investigations of the intramolecular hydrosilylation of homoallylic alcohols have not been reported.…”

Synthesis of Chiral Amines Using α‐Amino Aldehydes

“…Brown allylation has also been implemented in the asymmetric allylation of α‐amino aldehydes. In connection with their efforts toward the synthesis of the potent marine protein phosphatase inhibitor calyculin A, Barrett and Malecha48 subjected the Garner aldehyde to Brown allylation using ( d Ipc) 2 ‐ 30a , followed by Tamao oxidation49 to furnish the amino diol 33 in 57 % yield as a single diastereoisomer (Scheme ). The reaction proceeds as a matched case to afford the Felkin–Anh product with excellent diastereoselectivity.…”

Stereoselective Synthesis via Palladium-Catalyzed Intramolecular Bis-Silylation.

“…It is presumed that the insertion reaction proceeds through the "exo" complex, which involves less steric repulsion than the "endo" one (ref. 22). Indeed, the high diastereoselection in the intramolecular bis-silylation could lead to the stereoselective formation of the unstable transoxasiletanes 28, whose disproportionation gave the (E)-allylsilanes 26 and 6-membered cyclic 27.…”