141554-44-1Relevant articles and documents
Total Synthesis of Prostratin, a Bioactive Tigliane Diterpenoid: Access to Multi-Stereocenter Cyclohexanes from a Phenol
Ding, You-Song,Ding, Zhengwei,Li, Pengfei,Liu, Zhi,Tong, Guanghu,Xu, Liang,Zhang, Hailong
, p. 4813 - 4837 (2020/05/01)
Tiglianes such as prostratin and related diterpenoids are biologically significant natural molecules and long-standing targets for organic synthesis community. Due to the complex polycyclic scaffolds, high oxygenation level, and dense functional groups and stereocenters, their de novo chemical syntheses still face formidable challenges despite extensive efforts in the past 40 years. This account details the development of a modular and concise synthesis of prostratin, a potent anti-HIV and anticancer agent. The key approach in this synthesis involved a sequence of oxidative dearomatization and sequential stereoselective installation of peripheral groups to rapidly build the contiguously substituted cyclohexane C-ring. Inspired by Wender's work, an acid- A nd solvent-controlled stereodivergent formation of cyclopropane D-ring was developed. Mechanistic investigations by computational methods revealed that the competition between intra- A nd intermolecular hydrogen bonding led to different conformations, thus favoring different protonation processes. The designed and unexpected chemistry along this campaign reflected the uniqueness of the natural structures and should be amenable to future chemical syntheses of related complex polycyclic molecules.
Preparation of ecological catalysts derived from Zn hyperaccumulating plants and their catalytic activity in Diels-Alder reaction
Escande, Vincent,Olszewski, Tomasz K.,Grison, Claude
, p. 731 - 737 (2014/07/21)
Zn hyperaccumulating plants Noccaea caerulescens and Anthyllis vulneraria were used as the starting material for preparation of novel Lewis ecological catalysts. Those catalysts efficiently mediate the Diels-Alder reaction. High yields, very good regio- a
A route to enantiomerically pure 5-(2′-hydroxyethyl)cyclopent-2-en-1-ol and its absolute configuration by Mosher esters
Chen, Hao,Nagabandi, Srinivas,Smith, Steven,Goodman, Jonathan M.,Plettner, Erika
experimental part, p. 449 - 456 (2009/09/06)
The (±)-5-(2′-hydroxyethyl)cyclopent-2-en-1-ol 1 was prepared in a one-pot procedure, and was resolved using lipase AK and vinyl acetate with high ee. This provides a readily available chiral synthon for the synthesis of a wide variety of biologically int
Catalysis by lithium cation: Lithium trifluoromethanesulfonate as a substitute for lithium perchlorate in cycloadditions
Augé, Jacques,Gil, Richard,Kalsey, Sophie,Lubin-Germain, Nadège
, p. 877 - 879 (2007/10/03)
Lithium trifluoromethanesulfonate, an easily accessible lithium salt, is shown to be a safe alternative to lithium perchlorate as a promotor in organic Diels-Alder and hetero Diels-Alder reactions.
A facile synthesis of cis-9-[4-(1,2-dihydroxyethyl)-cyclopent-2-enyl]guanine and its derivative
An,Rhee
, p. 1111 - 1122 (2007/10/03)
The synthesis of carbocyclic nucleosides, cis-9-[4-(1,2-dihydroxyethyl)-cyclopent-2-enyl]guanine (3) and cis-2-amino-6-cyclopropylamino-9-[4-(1,2-dihydroxyethyl)-cyclopent-2-enyl]pur ine (4), was achieved from cyclopentadiene (5) in five and six steps, respectively. This route involves a hetero Diels-Alder reaction and a Pd(0)-catalyzed coupling reaction.
Enhancement of dienophilic and enophilic reactivity of the glyoxylic acid by bismuth(III) triflate in the presence of water
Laurent-Robert,Le Roux,Dubac
, p. 1138 - 1140 (2007/10/03)
Bismuth(III) trifluoromethanesulfonate (1) is found to efficiently catalyze carbonyl-Diels-Alder or carbonyl-ene reactions between glyoxylic acid and classical dienes or substituted olefins, in the presence of water.
Aqueous hetero Diels-Alder reactions: The carbonyl case
Lubineau,Auge,Grand,Lubin
, p. 10265 - 10276 (2007/10/02)
Commercially available aqueous solution of glyoxylic acid, pyruvaldehyde and glyoxal were shown to react with cyclic or non-cyclic dienes to give the corresponding cycloadducts and/or α-hydroxy γ-lactones. Activated ketone (Pyruvic acid) was shown to react as well in the same conditions.
Conversion of (-)-4-Hydroxy-2-oxabicyclooct-7-en-3-one into the anti-HIV Agent Carbovir
MacKeith, Rosemary A.,McCague, Ray,Olivo, Horacio F.,Palmer, Christopher F.,Roberts, Stanley M.
, p. 313 - 314 (2007/10/02)
The lactone (+/-)-1 was resolved using Pseudomonas fluorescens lipase and vinyl acetate; the ester (-)-3 obtained by this process was subsequently converted into the anti-HIV agent carbovir (-)-9.
Total Synthesis of (+/-)-Sesbanimide A and B
Grieco, Paul A.,Henry, Kenneth J.,Nunes, Joseph J.,Matt, James E.
, p. 368 - 370 (2007/10/02)
The total synthesis of sesbanimide A (1) and B (2) is reported which features (a) the reaction of cyclopentadiene with glyoxylic acid leading to the useful bicyclic lactone building block 3 and (b) the use of 2.5 mol/ dm-3 lithium perchlorate i
Hetero Diels-Alder Reaction in Water. Synthesis of α-Hydroxy-γ-Lactones
Lubineau, Andre,Auge, Jacques,Lubin, Nadege
, p. 7529 - 7530 (2007/10/02)
The hetero Diels-Alder reaction of cyclopentadiene or cyclohexadiene with aqueous solution of glyoxylic acid produces α-hydroxy-γ-lactones arising from the rearrangement of the cycloadducts.
