The Effect of Sulfoxides on the Stereoselective Construction of Tetrahydrofurans: Total Synthesis of (+)‐Goniothalesdiol

Hernández‐Torres, Gloria; Carreño, M. Carmen; Urbano, Antonio; Colobert, Françoise

doi:10.1002/chem.201002637

Cited by 16 publications

(2 citation statements)

References 94 publications

(64 reference statements)

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“…25,26 Further reduction of the Reformatsky adducts with DIBAL-H or DIBAL-H/Yb(OTf) 3 afforded with high diastereoselectivity the syn,syn stereotriad 30 or the syn,anti stereotriad 31, present in many natural products. 27 The removal or transformation of the chiral sulfoxide allowed us to apply this methodology to the total synthesis of biologically active molecules 28,29 (see Section 4.5).…”

Section: Synthesis Of 2-methyl-13-syn and Anti Diolsmentioning

confidence: 99%

Recent advances in the diastereoselective Reformatsky-type reaction

et al. 2013

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The classical Reformatsky reaction introduced for the first time in 1887 has been recognized as one among the most useful methods for C-C bond formation. Diastereoselective versions based on the use of chiral auxiliaries as well as enantioselective protocols using chiral ligands have been successfully developed during the last few years. This tutorial review highlights the main recent achievements (since 2004) in the diastereoselective Reformatsky reaction; diastereochemical control has been efficiently achieved using a large variety of chiral auxiliaries to perform the synthesis of specific cyclic and acyclic chiral moieties. The diastereoselective Reformatsky reactions employed in the total synthesis of natural products are also described.

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Section: Synthesis Of 2-methyl-13-syn and Anti Diolsmentioning

confidence: 99%

Recent advances in the diastereoselective Reformatsky-type reaction

et al. 2013

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“…In contrast, the 2,3-trans carbohydrate furanose derivatives present some discrepancies . For example, our group recently found that the stereochemistry in the C-glycosidations using Kishi’s protocol on d -fucose derivatives can be modulated by the protecting groups.…”

Section: Introductionmentioning

confidence: 99%

Stereocontrolled Nucleophilic Addition to Five-Membered Oxocarbenium Ions Directed by the Protecting Groups. Application to the Total Synthesis of (+)-Varitriol and of Two Diastereoisomers Thereof

et al. 2017

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A stereodivergent C-glycosidation of carbohydrate-derived lactones can be mediated by the protecting groups and applied to the total synthesis of (+)-varitriol and of two diastereoisomers thereof, which represent an unprecedent use of the protecting groups in the synthesis of a naturally occurring compound. In particular, the stereoselective nucleophile attack for 2,3-trans-substituted five-membered ring oxocarbenium ions is strongly influenced by the presence of aromatic rings in the protecting groups. According to quantum chemical calculations, the stereoselectvity depends on the π-π interactions between the aromatic ring of the C-2 protecting group with the exocyclic triple bond and the oxocarbenium ion. These interactions account for the stabilization of the conformer in which the C-2 and C-3 substituents adopt pseudoaxial orientations. When protecting groups do not contain an aromatic ring, the sterochemical outcome is dictated by stereoelectronic factors established by the Woerpel's model. Based on these findings, a concise total synthesis of the natural product (+)-varitriol and of two diastereoisomers was acomplished.

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