Toward the Synthesis of Spirastrellolide B:  A Synthesis of the C1−C23 Subunit

Keaton, Katie A.; Phillips, Andrew J.

doi:10.1021/ol702955m

Cited by 50 publications

(17 citation statements)

References 24 publications

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“…Phillips and co-workers prepared the spirastrellolide B C1-C23 subunit using the Cha modification [32] of the Kulinkovich reaction to combine two key fragments (Scheme 51). [112] Exposing alkene 196 and ester 197 to titanium(IV) isopropoxide and cyclohexylmagnesium bromide gave cyclopropanol 198 in 95 % yield as a single diastereomer. Radical fragmentation to ring-open the cyclopropanol afforded ketone 199 in 71 % yield.…”

Section: Synthesis Of Pharmaceuticals and Natural Productsmentioning

confidence: 99%

Modern Developments in the Chemistry of Homoenolates

Mills

Rousseaux

2018

Eur J Org Chem

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Homoenolates are unique synthetic intermediates which display umpolung reactivity. Homoenolates and homoenolate equivalents like cyclopropanols have seen a recent surge in popularity due to their particular utility for accessing β‐functionalized carbonyl derivatives. This popularity has been enabled by the development of protocols for facile access to cyclopropanols and homoenolates from a variety of readily available starting materials. This microreview will highlight common strategies for generating cyclopropanols and metal homoenolates, as well as procedures for homoenolate functionalization, with a particular emphasis on protocols that have appeared after 2003. As an amphoteric molecule, two main reactivity modes have been established: the homoenolate reacts as a carbon nucleophile for β‐functionalization reactions and/or as a carbonyl electrophile, a strategy which has only emerged in the past few years. This microreview will highlight the use of homoenolates as convenient intermediates for accessing especially challenging motifs. The use of homoenolate chemistry in the context of natural product and pharmaceutical synthesis will also be presented.

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Section: Synthesis Of Pharmaceuticals and Natural Productsmentioning

confidence: 99%

Modern Developments in the Chemistry of Homoenolates

Mills

Rousseaux

2018

Eur J Org Chem

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“…Several fragment syntheses of 141 have been reported by De Brabander, clxxviii Forsyth, clxxix Paterson, clxxx Hsung, clxxxi Furstner, clxxxii , Smith, clxxxiii and Phillips. clxxxiv Total syntheses of spirastrellolide A methyl ester and spirastrellolide F methyl ester have been accomplished by the Paterson clxxxv and Furstner clxxxvi groups, respectively.…”

Section: Selected Examplesmentioning

confidence: 99%

Integrated approaches to the configurational assignment of marine natural products

Molinski

Morinaka

2012

Tetrahedron

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“…Formation of linear ketones 4 (Z=H) is the simplest but a valuable radical transformation of cyclopropanols 1 , which was applied in several total syntheses of natural products at the crucial stage of subunits coupling . In the synthesis of (+)‐spirolaxine ( 10 ) reported by Phillips,[7a] ester and alkene fragments 5 and 6 were assembled by the Kulinkovich reaction to afford cyclopropanol 7 , which was further converted into the desired ketone 9 by means of the radical ring‐opening. Although formally this reaction is a rearrangement, it proceeds through two separate stages, each of which requires stoichiometric amounts of reagents, an oxidant and an H‐atom source, respectively.…”

Section: Introductionmentioning

confidence: 99%