Homologation of allylic alcohols. An approach to cyclic and acyclic polyoxygenated compounds

Divalent and Multivalent Activation in Phosphate Triesters: A Versatile Method for the Synthesis of Advanced Polyol Synthons

“…[9b] First, treatment of 5 with a sulfur ylide, generated in situ, gave allylic alcohol ( S )- 6 in excellent yield on multigram scale. [14] After generation of the corresponding alkoxide, condensation with (MeO)POCl 2 yielded a phosphate triester, which underwent ring-closing metathesis (RCM) with Grubbs second-generation catalyst cat- B (Figure 5) to afford cyclic phosphate ( S,S )- 1 . [15] …”

“…Diol 21 was accessed from dichloro-1,3- anti -diol 20 , [19] by using a modified Mioskowski-Christie protocol. [14] Condensation with POCl 3 , followed by coupling with a lithium alkoxide derived from allyl alcohol, gave triene 22 in good yields. Differentiation of the vinyl groups occurs through RCM (cat- B , CH 2 Cl 2 , 40°C) where the chair conformer bearing the allyl ester cis to the vinyl group leads to formation of a single chiral, nonracemic bicyclic product ( S,S,P R )- 4 .…”

Phosphate Tether-Mediated Approach to the Formal Total Synthesis of (−)-Salicylihalamides A and B

“…1,3- anti -diol 8 10 was desymmetrized using a phosphate tether-mediated RCM reaction to construct the P -chiral bicyclo[4.3.1]phosphate 7 (Scheme 2). 5 In this strategy, pseudo- C2 -symmetric phosphate triester 9 was synthesized from a 2-step sequential tripodal coupling 5c of diol 8 and allyl alcohol with POCl 3 or via a one-pot diol coupling with allyl tetraisopropylphosphorodiamidite followed by oxidation.…”

Synthesis of allylic alcohols from alkenes and their derivatives

“…Evidently, DMSM serves as the source of an additional carbon atom. 30,31 Since the oxidation state of the starting compound does not change upon the reaction, this reaction should be classified as isohypsic.…”