The Total Synthesis of Spiroketal‐Containing Natural Products

Vaillancourt, Valerie; Pratt, Norman E.; Perron, F.; Albizati, Kim F.

doi:10.1002/9780470129715.ch4

Cited by 13 publications

(21 citation statements)

References 215 publications

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“…Spiroketals are molecular frameworks found in a variety of complex natural products that possess a wide range of biological activities 50–57. Promising pharmacological effects (such as phosphatase inhibition, modulation of the tubulin cytoskeleton of breast cancer cells, and cytotoxic against tumor cell lines) have been discovered in the course of screening of simple spiroketals 58–67.…”

Section: Resultsmentioning

confidence: 99%

Reaction of selenium and tellurium halides with propargyl alcohols. The regio‐ and stereoselectivity of addition to the triple bond

Braverman

Cherkinsky

Jana

et al. 2010

J of Physical Organic Chem

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A convenient method to incorporate selenium into an organic molecule is reported. Various aspects of the reaction of SeCl2 with propargyl alcohols, i.e., identity of reacting functionality, regiospecificity, and stereospecificity, differ from expectations based on known reactions of these alcohols with SCl2. Selenium dihalides undergo smooth 1,2‐addition to the triple bond of various propargylic alcohols resulting in the formation of the corresponding functionalized divinyl selenides in high yields and with complete regio‐ and stereospecificity. Of special mechanistic interest is the syn‐addition and anti‐Markovnikov orientation observed in all cases. Copyright © 2010 John Wiley & Sons, Ltd.

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Section: Resultsmentioning

confidence: 99%

Reaction of selenium and tellurium halides with propargyl alcohols. The regio‐ and stereoselectivity of addition to the triple bond

Braverman

Cherkinsky

Jana

et al. 2010

J of Physical Organic Chem

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“…While many synthetic methods have been developed for the synthesis of spiroketal systems, 16 less attention has been devoted to the synthesis of oxaspirolactones and few synthetic methods exist. Early methods rely on special reagents, 17 stoichiometric transition metals to form reactive intermediates, 18 or several protection-deprotection steps to make appropriate hydroxyl ketoacids for acid-promoted cyclizations (cf.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Carbonylative Spirolactonization of Hydroxycyclopropanols

et al. 2016

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A palladium-catalyzed cascade carbonylative spirolactonization of hydroxycyclopropanols has been developed to efficiently synthesize oxaspirolactones common to many complex natural products of important therapeutic value. The mild reaction conditions, high atom economy, broad substrate scope, and scalability of this new method were highlighted in expedient total syntheses of the Turkish tobacco natural products α-levantanolide and α-levantenolide in two and four steps respectively. The hydroxycyclopropanol substrates are readily available in one step via a Kulinkovich reaction of the corresponding lactones. Mechanistic studies utilizing high-resolution electrospray ionization mass spectrometry (ESI-MS) identified several key intermediates in the catalytic cycle as well as those related to catalyst decomposition and competitive pathways.

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“…Berkelic acid (1) consists of a novel aromatic 5,6spiroketal embedded in a highly substituted tetracyclic framework. Berkelic acid (1) was recently isolated from a fungal extremophile, a Penicillium species, found in a highly acidic and metal-contaminated abandoned copper mine in Montana, USA. 3 Berkelic acid (1) exhibits selec-tive activity towards OVCAR-3, an ovarian cancer cell line.…”

Section: Figure 1 Monobenzannulated Spiroketal-containing Natural Productsmentioning

confidence: 99%

“…1,2 An interesting subgroup of aromatic spiroketals include the monobenzannulated spiroketals such as berkelic acid (1) 3 and chaetoquadrin A (2,4 Figure 1). …”

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A Novel Approach to Monobenzannulated Spiroketals Using Styrenes in the Kulinkovich Reaction

Haym¹,

Brimble²

2009

Synlett

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The synthesis of a series of 5,6-monobenzannulated spiroketals is reported. The use of various styrenes in a Kulinkovich reaction with an appropriately functionalized aliphatic ester affords cyclopropanol products which under basic conditions underwent ring opening to form ketone precursors to the spiroketals. Deprotection of the hydroxyl groups and subsequent cyclization afforded monobenzannulated spiroketals related to the core structure of berkelic acid.

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The Total Synthesis of Spiroketal‐Containing Natural Products

Cited by 13 publications

References 215 publications

Reaction of selenium and tellurium halides with propargyl alcohols. The regio‐ and stereoselectivity of addition to the triple bond

Reaction of selenium and tellurium halides with propargyl alcohols. The regio‐ and stereoselectivity of addition to the triple bond

Catalytic Carbonylative Spirolactonization of Hydroxycyclopropanols

A Novel Approach to Monobenzannulated Spiroketals Using Styrenes in the Kulinkovich Reaction

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