Enantioselective Synthesis of (+)-Crocacin C. An Example of a Highly Challenging Mismatched Double Asymmetric δ-Stannylcrotylboration Reaction

Chen, Ming; Roush, William

doi:10.1021/ol300476f

Cited by 30 publications

(13 citation statements)

References 34 publications

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“…The allylation reaction of α-branched chiral aldehyde (2 R ,3 S )- 1j , with 2a was carried out in the absence and presence of TRIP (5.0 mol %) (eq ). In the absence of TRIP, syn , anti - 3ja (highlighted in gray) was formed in 42% total yield with 88:12 diastereoselectivity ( 3ja / 3ja′ ) together with 24% (NMR yield) of ( E )- syn , anti -homoallylic alcohol 4ja .…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Synthesis of anti-1,2-Oxaborinan-3-enes from Aldehydes and 1,1-Di(boryl)alk-3-enes Using Ruthenium and Chiral Phosphoric Acid Catalysts

et al. 2017

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A cationic ruthenium(II) complex catalyzes double-bond transposition of 1,1-di(boryl)alk-3-enes to generate in situ 1,1-di(boryl)alk-2-enes, which then undergo chiral phosphoric acid catalyzed allylation of aldehydes producing homoallylic alcohols with a (Z)-vinylboronate moiety. 1,2-Anti stereochemistry is installed in an enantioselective manner. The (Z)-geometry forged in the products allows their isolation in a form of 1,2-oxaborinan-3-enes, upon which further synthetic transformations are operated.

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Section: Resultsmentioning

confidence: 99%

Enantioselective Synthesis of anti-1,2-Oxaborinan-3-enes from Aldehydes and 1,1-Di(boryl)alk-3-enes Using Ruthenium and Chiral Phosphoric Acid Catalysts

et al. 2017

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“…Since the first total synthesis in 2000 [39], a plethora of formal and total syntheses of the crocacin family have been developed, most of them taking advantage of a chiral-auxiliary-based aldol reaction to install the first syn stereocenter (for recent total syntheses see [40–43]).…”

Section: Resultsmentioning

confidence: 99%

Reiterative epoxide-based strategies for the synthesis of stereo-n-ads and application to polypropionate synthesis. A personal account

Cruz-Montañez

Morales-Rivera

Torres

et al. 2017

Inorganica Chimica Acta

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The enantioselective synthesis of polypropionates continues to be an attractive realm for the synthetic chemists mostly due to the challenges presented by the number of consecutive stereogenic centers contained within the aliphatic chain. Over the years, our laboratory has developed an epoxide-based three-step reiterative methodology for the construction of these targets, with the ultimate goal that the approach could be extended to the synthesis of polypropionate-containing natural products. The key steps include the diastereoselective epoxidation of allylic and homoallylic alcohols, and the regioselective cleavage of 2-methyl-3,4-epoxy alcohols. The choice of the organometallic reagent, and the cis/trans geometry of the chiral epoxide can be used to control both the relative and absolute configuration of the resulting propionate unit, allowing our approach to be applied in the synthesis of advanced fragments. Additionally, the combination of our first- and second-generation methodologies permits the incorporation of different variations at the methyl moiety.

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“…The formed C−O linkage had syn orientation relative to the existing stereocenter ( syn / anti =94:6). This diastereoselectivity is accounted for by assuming that the carbonyl addition mode conforms with the Felkin–Anh model, as with the case using ( E )‐crotyl pinacol boronate …”

Section: Figurementioning

confidence: 99%

Synthesis of γ‐Boryl‐Substituted Homoallylic Alcohols with anti Stereochemistry Based on a Double‐Bond Transposition

et al. 2018

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The stereoselective synthesis of anti isomers of γ‐boryl‐substituted homoallylic alcohols is disclosed. (E)‐1,2‐Di(boryl)alk‐1‐enes undergo Ru‐catalyzed double‐bond transposition with control of the geometry. The in situ generated (E)‐1,2‐di(boryl)alk‐2‐enes add to aldehydes in a stereospecific manner. The alkenylboron group within the product is amenable to a variety of synthetic derivatizations.

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Enantioselective Synthesis of (+)-Crocacin C. An Example of a Highly Challenging Mismatched Double Asymmetric δ-Stannylcrotylboration Reaction

Cited by 30 publications

References 34 publications

Enantioselective Synthesis of anti-1,2-Oxaborinan-3-enes from Aldehydes and 1,1-Di(boryl)alk-3-enes Using Ruthenium and Chiral Phosphoric Acid Catalysts

Enantioselective Synthesis of anti-1,2-Oxaborinan-3-enes from Aldehydes and 1,1-Di(boryl)alk-3-enes Using Ruthenium and Chiral Phosphoric Acid Catalysts

Reiterative epoxide-based strategies for the synthesis of stereo-n-ads and application to polypropionate synthesis. A personal account

Synthesis of γ‐Boryl‐Substituted Homoallylic Alcohols with anti Stereochemistry Based on a Double‐Bond Transposition

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