An Expeditious, Non‐Iterative, and Asymmetric Synthesis of 3,5,7,9,11,13,15‐Heptahydroxypentadecanals

Gerber‐Lemaire, Sandrine; Vogel, Pierre

doi:10.1002/ejoc.200300224

Cited by 19 publications

(11 citation statements)

References 46 publications

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“…Further elaboration of diacetate ( − )-50 delivered the semiprotected diol 51 which was submitted to a double ozonolysis followed by reduction of the intermediate ozonide and subsequent stereoselective reduction of the carbonyl moieties. [33] Interestingly, it was possible to isolate hemiketal 52, thus offering a chemical desymmetrization of the long chain polyketide. Further reduction delivered hexol 53 which revealed the C(5),C(7)anti and C(9),C(11)-syn configuration of the newly formed diols.…”

Section: From 11'-methylenedi(3-oxo-8-oxabicyclo[321]oct-6-ene) Tomentioning

confidence: 99%

Preparation and Synthetic Applications of 8-Oxabicyclo[3.2.1]oct-6-en-3-one Derivatives

Favre¹,

Gerber‐Lemaire²,

Vogel³

2008

Chimia

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The development of efficient routes to multi-gram quantities of chiral synthons is a key issue in the total synthesis of natural products and analogues. The conformationally defined and rigid 8-oxabicyclo[3.2.1]oct-6-en-3-one template is an appealing starting material for the development of non-iterative approaches to polyoxygenated fragments that are found in a large variety of biologically relevant natural compounds. Desymmetrization and resolution procedures, stereoselective functionalizations and double-chain elongations represent attractive strategies for such synthetic challenges.adducts. Further stereoselective functionalization of the rigid bicyclic templates then provides an efficient access to stereodefined polyketides. We give here an overview of noniterative approaches to polyoxygenated compounds from 8-oxabicyclo[3.2.1]oct-6-en-3-one derivatives that are generated through [4+3] cycloaddition reactions. [4+3]-Cycloadditions of Oxyallyl Cations to Furan and DerivativesThe generation of the 8-oxabicyclo[3.2.1]oct-6-en-3-one template can be achieved by a [4+3] cycloaddition of furan to oxyallyl cations of type 3 (Scheme 1). These stabilized cations 3 can be produced from tetrahalogenoketones 1 in the presence of a reducing metal [1] or a tertiary amine in an ionizing solvent. [2] The resulting rigid bicyclic system is a synthon of choice for stereoselective transformations as illustrated by the reduction of ketone 4 , with L-selectride or SmI 2 which provides the endo-alcohol 5 and the exo -alcohol 6 , respectively. In the late 1990s Vo gel and co-workers extended this powerful strategy to a double [4+3] cycloaddition of 2,2-methylenebis(furan) 7 to oxyallyl cations which gives rise to a mixture of bisbicycloadducts meso-8 and threo-8 in a 45:55 ratio (60% yield). [3] Several other precursors of oxyallyl cations were inves-

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Section: From 11'-methylenedi(3-oxo-8-oxabicyclo[321]oct-6-ene) Tomentioning

confidence: 99%

Preparation and Synthetic Applications of 8-Oxabicyclo[3.2.1]oct-6-en-3-one Derivatives

Favre¹,

Gerber‐Lemaire²,

Vogel³

2008

Chimia

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“…Kinetic resolution with Candida cylindracea lipase-catalyzed transesterification with vinyl acetate allows one to obtain enantiomerically enriched diacetate (+)-18 (98 % ee) and diol (-)-17 (98 % ee) [12]. Diacetate (+)-18 has been converted into (-)-19 (Scheme 3) [13] by the same procedure [9] as that converting meso-2 into 3 (Scheme 1). Double ozonolysis of (-)-19, followed by the diastereoselective reduction of the resulting double β-hydroxyketone intermediate applying Evans' [10] and Narasaka's [11] conditions allows the preparation of enantiomerically pure (98 % ee) polyols (-)-20 (65 %) and (-)-22 (60 %), respectively.…”

Section: Double Oxidative Cleavagementioning

confidence: 99%

“…Differentiation of the terminal centers of these 15-carbon polyketides is thus possible by control of temperature and excess of the reducing agent. For instance, pyranose (-)-21 can be isolated in 65 % yield from (-)-19 (Scheme 3) [13].…”

Section: Double Oxidative Cleavagementioning

confidence: 99%

Noniterative approach to the total asymmetric synthesis of 15-carbon polyketides and analogs with high stereodiversity

Vogel

Gerber‐Lemaire

Carmona

et al. 2005

Pure and Applied Chemistry

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Starting from inexpensive furan and furfuryl alcohol, a noniterative approach to the synthesis of pentadeca-1,3,5,7,9,11,13,15-octols and their derivatives has been developed. The method relies upon the double [4+3]-cycloaddition of 1,1,3-trichloro-2-oxylallyl cation with 2,2'-methylenedifuran and conversion of the adducts into meso and (±)-threo-1,1'-methylenebis (cis-and trans-4,6-dihydroxycyclohept-1-ene) derivatives. The latter undergo oxidative cleavage of their alkene moieties, generating 5-hydroxy-7-oxoaldehydes that are reduced diastereoselectively into either syn or anti-5,7-diols. Asymmetry is realized using either chiral desymmetrization with Sharpless asymmetric dihydroxylation or by kinetic resolution of polyols using lipase-catalyzed acetylations. All of the possible stereomeric pentadeca-1,3,5,7,9,11,13,15-octols and derivatives can be obtained with high stereoselectivity applying simple operations, thus demonstrating the high stereodiversity of this new, noniterative approach to the asymmetric synthesis of long-chain polyketides.

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“…Imidazole (5 equiv., 2.34 g, 34.41 mmol) and chlorotriethylsilane (3 equiv., 3.5 mL, 20 64 mmol) were added at 0°C to a solution of (Ϫ)-8 [15] (3.5 g, 6.881 mmol) in DMF (70 mL). After stirring at 0°C for 45 min, the mixture was poured into H 2 O (150 mL) and extracted with diethyl ether (100 mL, 3 times).…”

Section: (4r4јr6r6јr)-44ј-bis(benzyloxy)methoxy-66ј-bis(triethylmentioning

confidence: 99%

An Expeditious Asymmetric Synthesis of Polyfunctional 1,7‐Dioxaspiro[5.5]undecanes

Gerber‐Lemaire

Vogel

2004

Eur J Org Chem

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Quick access to polyfunctional spiroketal (3R)‐4[(2S,6R,8R,10S)‐4,4‐bis(ethylthio)‐10‐hydroxy‐8‐(2‐hydroxyethyl)‐1,7‐dioxaspiro[5.5]undec‐2‐yl]butane‐1,3‐diol [(+)‐19] is now available through the stereoselective functionalization of enantiomerically pure protected tetrol (4R,4′R,6R,6′R)1,1′‐methylenebis[4‐[(benzyloxy)methoxy]‐6‐[(triethylsilyl)oxy]cyclohept‐1‐ene [(−)‐9], derived from 2,2′‐methylenedifuran. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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An Expeditious, Non‐Iterative, and Asymmetric Synthesis of 3,5,7,9,11,13,15‐Heptahydroxypentadecanals

Cited by 19 publications

References 46 publications

Preparation and Synthetic Applications of 8-Oxabicyclo[3.2.1]oct-6-en-3-one Derivatives

Preparation and Synthetic Applications of 8-Oxabicyclo[3.2.1]oct-6-en-3-one Derivatives

Noniterative approach to the total asymmetric synthesis of 15-carbon polyketides and analogs with high stereodiversity

An Expeditious Asymmetric Synthesis of Polyfunctional 1,7‐Dioxaspiro[5.5]undecanes

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