Relevance of Conformational Constraints to the Regioselective Lithiation of Aromatic Diethers. Application to the Convenient Construction of the DEF Tricyclic Subunit of the Austalides

Paquette, Leo A.; Schulze, Matthias; Bolin, David G.

doi:10.1021/jo00087a018

Cited by 30 publications

(8 citation statements)

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“…Thus, TIPS-protected ribal 6 underwent C1-formylation and reduction to provide hydroxymethyl ribal 7 , which was then converted to iodide 8 (Figure ) . The pyrrole dicarboxaldehyde 9 , was then coupled under biphasic conditions to afford the key pyrrologlycal 10 .…”

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confidence: 99%

Stereoselective Synthesis of Acortatarins A and B

2012

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Acortatarins A and B have been synthesized via stereoselective spirocyclizations of glycals. Mercury-mediated spirocyclization of a pyrrole monoalcohol sidechain leads to acortatarin A. Glycal epoxidation and reductive spirocyclization of a pyrrole dialdehyde sidechain leads to acortatarin B. Acid equilibration and crystallographic analysis indicate that acortatarin B is a contrathermodynamic spiroketal with distinct ring conformations compared to acortatarin A.

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confidence: 99%

Stereoselective Synthesis of Acortatarins A and B

2012

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“…13 Our plan was to lithiate 26-28 at the enol ether α position using the method of Paquette, which was the most closely related precedent, and formylate them to afford the derived aldehydes. 14,15 Reduction or oxidation 16 would provide the alcohols or acids respectively.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of a Family of Spirocyclic Scaffolds: Building Blocks for the Exploration of Chemical Space

et al. 2013

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This report describes the preparation of a series of 17 novel racemic spirocyclic scaffolds that are intended for the creation of compound libraries by parallel synthesis for biological screening. Each scaffold features two points of orthogonal diversification. The scaffolds are related to each other in four ways: Through stepwise changes in the size of the nitrogen bearing ring.Through the oxidation state of the carbon centered point of diversification.Through the relative stereochemical orientation of the two diversification sites in those members that are stereogenic.Through the provision of both saturated and unsaturated versions of the furan ring in the scaffold series derived from 3-piperidone. The scaffolds provide incremental changes in the relative orientation of the diversity components that would be introduced onto them. The scaffolds feature high sp3 carbon content which is essential for the three dimensional exploration of chemical space. This characteristic is particularly evident in those members of this family that bear two stereocenters, i.e. the two series derived from 3-piperidone and 3-pyrrolidinone. In the series derived from 3-piperidone we were able to “split the difference” between the two diastereomers by preparation of their corresponding unsaturated version.

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“…High-resolution mass spectra were obtained in-house or from Washington University Resource for Biomedical/Bio-organic Mass Spectrometry (St. Louis, MO). Compounds 5 ,18b 11 , 12 , 14 , 16 , 17 , 18 , and 25 were all prepared from literature procedures.…”

Section: Methodsmentioning

confidence: 99%

“…Our initial effort involves the benzannulation between α,β-unsaturated glycosylated chromium carbene complexes 7 and 8 and trimethylsilylacetylene (Scheme ). Metalation of dihydropyran or tri-OTBDPS- d -glucal with tert -butyllithium followed by the addition of DMF gives the required C-1 glycosyl aldehydes 5 and 6 . Aldol condensation with the anion of [(methyl)(methoxy)carbene]pentacarbonylchromium(0) 4 gives the desired glycosylated carbene complexes .…”

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confidence: 99%