Asymmetric Total Synthesis of Solandelactone E: Stereocontrolled Synthesis of the 2‐ene‐1,4‐diol Core through a Lithiation–Borylation–Allylation Sequence

Robinson, Anna; Aggarwal, Varinder K.

doi:10.1002/anie.201003236

Cited by 50 publications

(11 citation statements)

References 38 publications

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“…The latter method is more direct and more versatile as it enables ready access to alternative stereoisomers. We (and others 15 , 16 , 17 , 18 ) have focussed on reagent-controlled methodology and we have found that Hoppe’s lithiated carbamate 19 , 20 , 21 homologate boronic esters with high stereocontrol and have applied this methodology in the synthesis of a number of natural products 22 , 23 , 24 , 25 , 26 . In order to apply this methodology to iterative homologations we set the goal of creating a carbon chain with 10 contiguous methyl substituents with total stereocontrol ( Figure 1b ).…”

Section: Development Of the Iterative Homologation Processmentioning

confidence: 97%

Assembly-line synthesis of organic molecules with tailored shapes

Burns

Essafi

Bame

et al. 2014

Nature

279

157

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Molecular assembly lines, where molecules undergo iterative processes involving chain elongation and functional group manipulation are hallmarks of many processes found in Nature. We have sought to emulate Nature in the development of our own molecular assembly line through iterative homologations of boronic esters. Here we report a reagent (α-lithioethyl triispopropylbenzoate) which inserts into carbon-boron bonds with exceptionally high fidelity and stereocontrol. Through repeated iteration we have converted a simple boronic ester into a complex molecule (a carbon chain with ten contiguous methyl groups) with remarkably high precision over its length, its stereochemistry and therefore its shape. Different stereoisomers were targeted and it was found that they adopted different shapes (helical/linear) according to their stereochemistry. This work should now enable scientists to rationally design and create molecules with predictable shape, which could have an impact in all areas of molecular sciences where bespoke molecules are required.

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Section: Development Of the Iterative Homologation Processmentioning

confidence: 97%

Assembly-line synthesis of organic molecules with tailored shapes

Burns

Essafi

Bame

et al. 2014

Nature

279

157

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“…This chemistry has been applied to the stereocontrolled synthesis of the complex natural products (À)-decarestrictine D [21] and solandelactone E 33 [22] and F 34 [23]. The synthesis of the two solandelactones is instructive.…”

Section: Scheme 4 Chiral Diamines Used In Asymmetric Deprotonationmentioning

confidence: 98%

“…This resulted in the formation of the isomeric Z-anti-allyl silane 41 en route to the title compound 34 [22].…”

Section: Scheme 4 Chiral Diamines Used In Asymmetric Deprotonationmentioning

confidence: 99%

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Reagent-Controlled Lithiation–Borylation

Leonori

Aggarwal

2015

Synthesis and Application of Organoboron Compounds

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“…2 The syntheses of all solandelactones A-H have been reported. [2][3][4][5] Martin completed the first synthesis of solandelactone E in 2007, which was highly stereoselective, but linear and therefore somewhat lengthy. 2 Syntheses of the remaining solandelactones were subsequently reported by White 3 and Pietruszka, 4 who both opted for disconnections at C11-C12 and utilized a Nozaki-Hiyama-Kishi (NHK) reaction to complete the syntheses.…”

Section: Introductionmentioning

confidence: 99%

Stereocontrolled asymmetric synthesis of syn-E-1,4-diol-2-enes using allyl boronates and its application in the total synthesis of solandelactone F

Robinson

Aggarwal

2012

Org. Biomol. Chem.

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The solandelactones A-H comprise a novel class of oxygenated fatty acids bearing an eight-membered lactone, trans cyclopropane, and a 2-ene-1,4-diol subunit. The relative stereochemistry of the 1,4-diol subunit is anti in solandelactones A, C, E & G, and syn in solandelactones B, D, F & H. Having prepared one member of the solandelactones bearing anti stereochemistry (solandelactone E), we have targeted the syn series and developed methodology for the synthesis of enantioenriched syn-2-ene-1,4-diols. The methodology comprises asymmetric deprotonation of an alkyl 2,4,6-triisopropylbenzoate using sBuLi/sparteine, followed by addition of the α-lithiobenzoate to β-silyl vinyl boronic acid ethylene glycol ester. The boron-ate complex generated undergoes a 1,2-metallate rearrangement furnishing an intermediate allyl boronic ester which is trapped by an aldehyde in the presence of MgBr(2) to furnish anti-β-hydroxy E-allylsilanes in good yields, high diastereoselectivity and high enantioselectivity. These sensitive products were oxidized using mCPBA to the corresponding epoxides and subsequently treated with acid to furnish syn-E-2-ene-1,4-diols (~4:1 d.r.). Application of the methodology to appropriately functionalized aldehyde and ω-alkenyl 2,4,6-triisopropylbenzoate coupling partners, led to a short, highly selective route to solandelactone F (bearing a syn-E-2-ene-1,4-diol).

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Asymmetric Total Synthesis of Solandelactone E: Stereocontrolled Synthesis of the 2‐ene‐1,4‐diol Core through a Lithiation–Borylation–Allylation Sequence

Cited by 50 publications

References 38 publications

Assembly-line synthesis of organic molecules with tailored shapes

Assembly-line synthesis of organic molecules with tailored shapes

Reagent-Controlled Lithiation–Borylation

Stereocontrolled asymmetric synthesis of syn-E-1,4-diol-2-enes using allyl boronates and its application in the total synthesis of solandelactone F

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