Chemistry of spiroketals

Perron, F.; Albizati, Kim F.

doi:10.1021/cr00097a015

Cited by 645 publications

(326 citation statements)

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“…P olyketide biosynthetic units are ubiquitous among natural products of diverse origin (1)(2)(3)(4)(5). Although the more common ones constitute hydroxy stereotriads originating from the condensation of propionyl-CoA biogenetic precursors (6), a small subgroup harbors deoxygenated motifs, commonly known as deoxypropionates.…”

mentioning

confidence: 99%

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Hanessian

Mascitti

Giroux

2004

Proc. Natl. Acad. Sci. U.S.A.

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The total synthesis of the marine cyclodepsipeptide (؊)-doliculide is described. An acyclic (2S,4S,6R)-trimethyl alkanoic acid precursor to the ''hydrocarbon'' portion of doliculide was synthesized starting with L-ascorbic acid based on a stereocontrolled iterative conjugate addition of lithium dimethylcuprate to acyclic ␦-Cmethyl ␣,␤-unsaturated ester derivatives. syn͞syn selectivity was achieved by relying on 1,3-induction in preferred folded conformations that avoid 1,5-syn-pentane interactions in the transition states. The nature of the ester moiety seems to play an important role in determining the syn͞anti ratios of C-methyl adducts. The 1-methyl-1-cyclopentyl ester group was found to confer the best syn selectivity to the cuprate addition products, especially in seven-carbon enoates.

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confidence: 99%

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Hanessian

Mascitti

Giroux

2004

Proc. Natl. Acad. Sci. U.S.A.

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“…R f (50 % EtOAc/hexane, UV/PMA) = 0.41. 1 1 mixture, 20 mL). The phases were separated and the aqueous one was extracted four times with EtOAc (10 mL) and once with brine (10 mL) and dried with MgSO 4 .…”

Section: Methodsmentioning

confidence: 99%

“…[1] It is noteworthy that the configurations of the stereogenic carbon atoms in most of these structures are dictated by double anomeric effects, placing the oxygen in the oxolane ring axial with respect to the oxane ring ( Figure 1). [2] Because of the wide occurrence of such motifs, a rapid and reliable route to the spirocyclic structure is highly desirable.…”

Section: Introductionmentioning

confidence: 99%

The Reaction Mechanism of Spirocylization and Stereoselectivity Studies for the Calyculin C₁₆–C₂₅ Fragment

Rauhala

Nättinen²,

Koskinen

2005

Eur J Org Chem

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The mechanism of the double intramolecular hetero‐Michael addition, a key reaction in the planned synthesis of the natural product calyculin C, has been studied by NMR. The cyclization follows Baldwin’s rules and proceeds first through a six‐membered ring closure (6‐endo‐dig), followed by a five‐membered ring cyclization (5‐exo‐trig). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…1 The increasing pharmacological importance of compounds with spiroketal blocks has triggered intense interest in both preparation and chemical reactivity. A rigid spiroketal framework may provide pinpoint orientation of pendant functional groups, which facilitates interactions in complex biochemical systems.…”

Section: Introductionmentioning

confidence: 99%

Total synthesis of proposed cephalosporolides H and I

Zhao

et al. 2015

Tetrahedron

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a b s t r a c tAn efficient total synthesis toward spiroketal diastereomers of cephalosporolides H and I was achieved, respectively, taking advantage of intramolecular Wacker-type spiroketalization on the common olefincontaining dihydroxy-g-lactone substrate. By comparing the physical data of natural products with synthetic samples, we suggest that the reported stereochemical assignments for cephalosporolides H and I are incorrect. Our work suggests that the stereochemistry on C-6 of the core spiroketal skeleton should be revised to S from its original R assignment, and the real structures of these natural compounds should be reconsidered.

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Chemistry of spiroketals

Cited by 645 publications

References 34 publications

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

The Reaction Mechanism of Spirocylization and Stereoselectivity Studies for the Calyculin C₁₆–C₂₅ Fragment

Total synthesis of proposed cephalosporolides H and I

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Chemistry of spiroketals

Cited by 645 publications

References 34 publications

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

The Reaction Mechanism of Spirocylization and Stereoselectivity Studies for the Calyculin C16–C25 Fragment

Total synthesis of proposed cephalosporolides H and I

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The Reaction Mechanism of Spirocylization and Stereoselectivity Studies for the Calyculin C₁₆–C₂₅ Fragment