A carbohydrate approach for the formal total synthesis of the prostacyclin analogue (16S)-iloprost

Chandrasekhar, Srivari; Chirumarry, Sridhar; Srihari, P.

doi:10.1016/j.tetasy.2012.03.005

Cited by 6 publications

(5 citation statements)

References 29 publications

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“…Importantly, our method could successfully be applied to furnish enol silane 3w, which is a known intermediate toward the synthesis of the prostacyclin analogue iloprost, a commercial drug used for the treatment of pulmonary arterial hypertension. 30 As proposed above, our catalytic asymmetric ketone silylation reaction is likely driven by the irreversible protodesilylation of the allylsilane. We therefore hypothesized that, if a suitable proton source could be identified, a kinetic resolution of racemic enolsilanes may also be achievable with IDPi catalysts, in what is effectively the reverse of our enol silane synthesis.…”

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confidence: 83%

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confidence: 99%

“…All of these transformations proceeded smoothly to give products 5 – 9 , with complete conservation of the enantiomeric purity. Importantly, our method could successfully be applied to furnish enol silane 3w , which is a known intermediate toward the synthesis of the prostacyclin analogue iloprost , a commercial drug used for the treatment of pulmonary arterial hypertension …”

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confidence: 99%

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The Silicon–Hydrogen Exchange Reaction: A Catalytic σ-Bond Metathesis Approach to the Enantioselective Synthesis of Enol Silanes

et al. 2020

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The use of chiral enol silanes in fundamental transformations such as Mukaiyama aldol, Michael, and Mannich reactions as well as Saegusa–Ito dehydrogenations has enabled the chemical synthesis of enantiopure natural products and valuable pharmaceuticals. However, accessing these intermediates in high enantiopurity has generally required the use of either stoichiometric chiral precursors or stoichiometric chiral reagents. We now describe a catalytic approach in which strongly acidic and confined imidodiphosphorimidates (IDPi) catalyze highly enantioselective interconversions of ketones and enol silanes. These “silicon–hydrogen exchange reactions” enable access to enantiopure enol silanes via tautomerizing σ-bond metatheses, either in a deprotosilylative desymmetrization of ketones with allyl silanes as the silicon source or in a protodesilylative kinetic resolution of racemic enol silanes with a carboxylic acid as the silyl acceptor.

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The Silicon–Hydrogen Exchange Reaction: A Catalytic σ-Bond Metathesis Approach to the Enantioselective Synthesis of Enol Silanes

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“…1 H NMR (300 MHz, 3 ) δ 7.24 (d,J = 7.5 Hz,1H),7.08 (d,J = 8.3 Hz,1H),4.67 (d,J = 3.8 Hz,1H),1H),3.72 (s,3H),3H),1H),2H), 2.32 (s, 3H), 2.14-1.90 (m, 2H); 13 C NMR (75 MHz, CDCl 3 ) δ 173. 4,136.5,136.3,134.6,134.1,128.8,128.2,70.3,69.0,51.7,32.9,26.0,24.6,24.3,19.6;IR (KBr) 4,5,3]dioxol-6-yl)propanoate (15). To a solution of 14 (2.35 g, 8.89 mmol) in dry CH 2 Cl 2 (20 mL) was added NEt 3 (3.7 mL, 26.67 mmol).…”

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“…Nonetheless, the skeleton attracted our attention due to our interest in molecules with important biological activities, including the synthesis of prostanoids, beraprost (antiplatelet drug) 4 and iloprost (drug for pulmonary arterial hypertension). 5 We wish to explore a non-Diels-Alder approach for the synthesis of this molecule which can be further extended to synthesize analogues.…”

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Total synthesis of a thromboxane receptor antagonist, terutroban

et al. 2015

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TheJulia–Kocienski Olefination

Blakemore¹,

Sephton

Ciganek

2018

Organic Reactions

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The Julia–Kocienski olefination is a direct connective synthesis of alkenes via the addition of metalated aryl alkyl sulfones to carbonyl compounds. The activating aromatic group associated with the sulfone must possess electrophilic character, and alkene formation occurs via β‐alkoxy sulfone formation, transfer of the aryl group from sulfur to oxygen via a Smiles rearrangement, and then elimination of sulfur dioxide and an aryloxide anion from the resulting β‐aryloxy sulfinate anion. The olefination process itself and the methods used to prepare the requisite sulfone substrates are tolerant of a wide variety of functional groups, and a variety of alkene targets can be prepared. Stereoselectivity is dependent on the nature of the sulfone, the carbonyl compound, the activating aryl moiety, and the reaction conditions. This chapter describes theoretical and operational aspects of the Julia–Kocienski olefination such that the reader will be able to obtain optimal results in his/her own research. A detailed mechanistic overview is included to account for the factors that influence stereoselectivity and yield. Methods for introducing sulfone activators into fragments of interest, best practices for generating sulfone anions, and optimal strategies for targeting different classes of alkene targets are discussed. Functional group compatibilities, reaction variants, and a comparison to other methods of alkene synthesis are also presented. Tabular surveys are organized according to type of alkene synthesized, with an emphasis on the degree of substitution and the level of conjugation about the newly formed double bond. The literature is covered from the initial disclosure of the Julia–Kocienski olefination in 1991 to the first quarter of 2016.

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A carbohydrate approach for the formal total synthesis of the prostacyclin analogue (16S)-iloprost

Cited by 6 publications

References 29 publications

The Silicon–Hydrogen Exchange Reaction: A Catalytic σ-Bond Metathesis Approach to the Enantioselective Synthesis of Enol Silanes

The Silicon–Hydrogen Exchange Reaction: A Catalytic σ-Bond Metathesis Approach to the Enantioselective Synthesis of Enol Silanes

Total synthesis of a thromboxane receptor antagonist, terutroban

TheJulia–Kocienski Olefination

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