71325-97-8Relevant articles and documents
Stereopure 1,3-butadiene-2-carboxylates and their conversion into non-racemic α-alkylidenebutyrolactone natural products by asymmetric dihydroxylation
Harcken, Christian,Brückner, Reinhard
, p. 3967 - 3971 (2001)
Dienoic esters 1 with the four possible permutations of the C=C configurations were prepared in two steps via non-stereoselective aldol additions followed by stereospecific β-eliminations. Sharpless dihydroxylations of these esters yielded natural and unnatural α-alkylidene-β-hydroxybutyrolactones 2. Among these were synthetic dihydromahubanolide B (cis,Z-2a), isodihydromahubanolide B (cis,E-2a) and, for the first time, litsenolide D1 (ent-trans,Z-2b) and the enantiomer trans,E-2b of litsenolide D2. Competitively, dihydroxyesters 10 were formed.
(Z)-3-alkylidene-4,5-dihydro-4-hydroxy-5-methyl-2-(3H)-furanones by regio- and diastereoselective ene reaction of singlet oxygen (Schenk reaction) with γ-hydroxy vinylstannanes: An enantioselective synthesis of dihydromahubanolide B
Adam,Klug
, p. 567 - 572 (2007/10/02)
(Z)-3-Alkylidene-4,5-dihydro-4-hydroxy-5-methyl-2-(3H)-furanones 5 were prepared from appropriately substituted propargylic alcohols 1 by a sequence of hydromagnesation to γ-hydroxy vinylstannanes 2, subsequent photooxygenation and reduction to stannyl diols 3, iododestannylation to iodo diols 4, and finally cyclization by palladium-catalyzed carbonylation (for 5a) or Ni(CO)2(PPh3)2 (for 5b,c). The reaction sequence can be performed enantioselectively by starting with chiral propargylic alcohols. The current approach constitutes a convenient four-step synthesis of optically active lactones 5 from readily available starting materials and is applied herein to the preparation of the natural lactone dihydromahubanolide B.
The Total Synthesis of Lauraceae Lactones: Obtusilactones, Litsenolides, and Mahubanolides
Rollinson, Susan Wells,Amos, Richard A.,Katzenellenbogen, John A.
, p. 4114 - 4125 (2007/10/02)
The total synthesis of obtusilactones (1a,b, 2a,b), mahubanolides (1c, 2c), epilitsenolides (5b, 6b), and dihydromahubanolides (4c, 5c, 6c) is described.The enolates derived from the α-phenylselenenyl esters (17a-c) were used as acrylate α-anion synthons; aldol addition to propargylaldehyde, followed by oxidation to the selenoxide and elimination, furnished the isomeric acetylenic esters 20a-c and 21a-c.In a similar manner, aldol addition to acrolein followed by oxidation/elimination yielded olefinic esters 18b,c and 19b,c.The acetylenic esters were saponified, and the corresponding carboxylic acids were converted by either mercuric ion-catalyzed or bicarbonate-catalyzed lactonization to the obtusilactones (1a,b, 2a,b) and mahubanolides (1c, 2c).The olefinic esters were saponified, and the corresponding carboxylic acids lactonized to γ-substituted lactones (30b,c, 32b,c 32c) by treatment with either phenylselenenyl chloride or iodine.The epilitsenolides (5b, 6b) and dihydromahubanolides (5c, 6c) were then obtained by treating the substituted γ-lactones with tri-n-butyltin hydride.Homogeneous catalytic hydrogenation (Rh(PPh3)3Cl) of isomahubanolide (2c) gave a mixture of dihydromahubanolides 4c and 6c.