61229-00-3Relevant articles and documents
Synthesis of prostaglandin and phytoprostane B1 via regioselective intermodular pauson-khand reactions
Vazquez-Romero, Ana,Cardenas, Lydia,Blasi, Emma,Verdaguer, Xavier,Riera, Antoni
, p. 3104 - 3107 (2009)
A new approach to the synthesis of prostaglandin and phytoprostanes B 1 is described. The key step is an intermolecular Pauson-Khand reaction between a silyl-protected propargyl acetylene and ethylene. This reaction, promoted by NMO in the presence of 4 A molecular sieves, afforded the 3-fert-butyldimethylsilyloxymethyl-2-substituted-cyclopent-2-en-1- ones (III) in good yield and with complete regioselectivity. Deprotection of the silyl ether, followed by Swern oxidation, gave 3-formyl-2-substituted- cyclopent-2-en-1-ones (II). Julia olefination of the aldehydes II with the suitable chiral sulfone enabled preparation of PPB1 type I and PGB1.
Concise, scalable and enantioselective total synthesis of prostaglandins
Zhang, Fuhao,Zeng, Jingwen,Gao, Mohan,Wang, Linzhou,Chen, Gen-Qiang,Lu, Yixin,Zhang, Xumu
, p. 692 - 697 (2021/06/01)
Prostaglandins are among the most important natural isolates owing to their broad range of bioactivities and unique structures. However, current methods for the synthesis of prostaglandins suffer from low yields and lengthy steps. Here, we report a practicability-oriented synthetic strategy for the enantioselective and divergent synthesis of prostaglandins. In this approach, the multiply substituted five-membered rings in prostaglandins were constructed via the key enyne cycloisomerization with excellent selectivity (>20:1 d.r., 98% e.e.). The crucial chiral centre on the scaffold of the prostaglandins was installed using the asymmetric hydrogenation method (up to 98% yield and 98% e.e.). From our versatile common intermediates, a series of prostaglandins and related drugs could be produced in two steps, and fluprostenol could be prepared on a 20-gram scale. [Figure not available: see fulltext.]
Synthesis of the C(7)-C(22) Sector of (+)-Acutiphycin via O-directed double free radical alkyne hydrostannation with Ph3SnH/Et3B, double I-Sn exchange, and double stille coupling
Hale, Karl J.,Maczka, Maciej,Kaur, Amarjit,Manaviazar, Soraya,Ostovar, Mehrnoosh,Grabski, Milosz
, p. 1168 - 1171 (2014/03/21)
Herein a new double O-directed free radical hydrostannation reaction is reported on the structurally complex dialkyldiyne 11. Through our use of a conformation-restraining acetal to help prevent stereocenter-compromising 1,5-H-atom abstraction reactions b
Asymmetric hydroformylation of Z -Enamides and enol esters with rhodium-bisdiazaphos catalysts
Abrams, M. Leigh,Foarta, Floriana,Landis, Clark R.
, p. 14583 - 14588 (2015/01/08)
Asymmetric hydroformylation (AHF) of Z-enamides and Z-enol esters provides chiral, alpha-functionalized aldehydes with high selectivity and atom economy. Rh-bisdiazaphospholane catalysts enable hydroformylation of these challenging disubstituted substrates under mild reaction conditions and low catalyst loadings. The synthesis of a protected analog of l-DOPA demonstrates the utility of AHF for enantioselective, atom-efficient synthesis of peptide precursors.
From enantiopure hydroxyaldehydes to complex heterocyclic scaffolds: Development of domino Petasis/diels-alder and cross-metathesis/Michael addition reactions
Cannillo, Alexandre,Norsikian, Stéphanie,Tran Huu Dau, Marie-Elise,Retailleau, Pascal,Iorga, Bogdan I.,Beau, Jean-Marie
, p. 12133 - 12143 (2015/03/31)
One-step assembly of hexahydroisoindole scaffolds by a sequence that combines the Petasis (borono-Mannich) and Diels-Alder reactions is described. The unique selectivity observed experimentally was confirmed by quantum calculations. The current method is
Fast synthesis of complex enantiopure heterocyclic scaffolds by a tandem sequence of simple transformations on α-hydroxyaldehydes
Cannillo, Alexandre,Norsikian, Stephanie,Retailleau, Pascal,Dau, Marie-Elise Tran Huu,Iorga, Bogdan I.,Beau, Jean-Marie
supporting information, p. 9127 - 9131 (2013/07/26)
Two tandems are faster than one! Properly sequenced reactions initiated by the Petasis aminoalcohol synthesis from boronic acids, diallylamine, and α-hydroxyaldehydes, including free aldoses, leads to rapid construction of complex enantiopure structures (see scheme). Copyright
Synthesis of substituted α,β-unsaturated δ-lactones from vinyl tellurides
Oliveira, Juliana M.,R. Freitas, Juliano C.,Comasseto, Jo?o Valdir,Menezes, Paulo Henrique
experimental part, p. 3003 - 3009 (2011/04/27)
A new approach for the synthesis of α,β-unsaturated δ-lactones, a unit present in many natural products with interesting biological activities is described. The approach was based on the use of a vinyl telluride, and it is complementary to the methods usi
A route to 1,2-diols by enantioselective organocatalytic α-oxidation with molecular oxygen
Ibrahem, Ismail,Zhao, Gui-Ling,Sundén, Henrik,Córdova, Armando
, p. 4659 - 4663 (2007/10/03)
A route to 1,2-diols by the direct organocatalytic enantioselective α-oxidation of aldehydes using molecular oxygen is presented. Protected commercially available chiral pyrrolidines catalyze the asymmetric α-oxidation of aldehydes with singlet molecular oxygen with high enantioselectivity to furnish the corresponding diols after in situ reduction in high yield with up to 98% ee. Electrophilic singlet molecular oxygen was photo or chemically generated ('dark' 1O2).
Syntheses of the macrolide subunits of merremoside-type resin glycosides
Zhu, Xing-Mei,He, Li-Li,Yang, Guang-Li,Lei, Ming,Chen, Si-Shi,Yang, Jin-Song
, p. 3510 - 3512 (2007/10/03)
The 20- and 21-membered macrolide subunits of merremoside-type resin glycosides with interesting bioactivity were synthesized via a macrolactonization approach using Corey-Nicolaou protocol in 14 steps with overall yields of 0.7% for 17 and 3.5% for 18 fr
Catalytic enantioselective hydrogenation of vinyl bis(boronates)
Morgan, Jeremy B.,Morken, James P.
, p. 15338 - 15339 (2007/10/03)
Catalytic enantioselective hydrogenation of prochiral vinylmetallic reagents can provide an attractive alternative to hydrometalation and bismetalation of alkenes. In this contribution, the first highly enantioselective hydrogenation of vinyl boronic esters is described. The chiral reduction products are versatile intermediates for chemical synthesis. Copyright
