Unprecedented stereoselectivity in a reaction of a novel diboron compound ? 1,6-bis(dialkylboryl)-2,4-hexadiene with carbonyl compounds

Gursky, M. E.; Geiderikh, A. V.; Игнатенко, А. В.; Bubnov, Yu. N.

doi:10.1007/bf00699997

Cited by 6 publications

(5 citation statements)

References 6 publications

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“…By judicious choice of reaction conditions, a single allyl transfer could also be effected, and the remaining allylboron group be used as a handle for further functionalization. Bubnov first reported a highly reactive 1,6‐diborane and demonstrated its two‐fold addition to acetaldehyde, which resulted in a mixture of diastereoisomers . Because the reagent preparation required the use of pyrophoric dialkylhaloboranes, its use has been limited .…”

Section: Methodsmentioning

confidence: 99%

“…Bubnov first reported a highly reactive 1,6‐diborane and demonstrated its two‐fold addition to acetaldehyde, which resulted in a mixture of diastereoisomers . Because the reagent preparation required the use of pyrophoric dialkylhaloboranes, its use has been limited . For our purposes, we required a reagent that could be accessed on a large scale and exhibited predictable reactivity and stereoselectivity.…”

Section: Methodsmentioning

confidence: 99%

“…[15] Because the reagent preparation required the use of pyrophoric dialkylhaloboranes,i ts use has been limited. We envisioned that the symmetric nature of such ar eagent would make it uniquely suited for bidirectional synthetic approaches involving two-fold aldehyde addition.…”

mentioning

confidence: 99%

“…Bubnov first reported ahighly reactive 1,6-diborane and demonstrated its two-fold addition to acetaldehyde,which resulted in amixture of diastereoisomers. [15] Because the reagent preparation required the use of pyrophoric dialkylhaloboranes,i ts use has been limited. [15] Foro ur purposes,w er equired ar eagent that could be accessed on al arge scale and exhibited predictable reactivity and stereoselectivity.A st he isomeric purity and stability of allylboron reagents is critical to their synthetic utility,w ed ecided to focus on pinacol boronate esters,which led us to bis-allylboronate 1 (Scheme 2).…”

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confidence: 99%

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A Versatile Bis‐Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols

et al. 2018

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Allylboron reagents are popular in synthesis owing to their versatility and the predictable stereochemical outcomes of their reactions with carbonyl compounds. Herein, we describe the synthesis of (Z,Z)-hexadienyl bis-boronate 1, a configurationally stable, crystalline, and easy to handle compound, which represents a class of bis-allylic boron reagents with heretofore untapped synthetic potential. In combination with a chiral phosphoric acid catalyst, the reagent can be employed for the enantioselective allyl transfer reaction to a variety of one-pot transformations, enabling swift access to functionalized 1,n-diols. The in situ conversion of the reagent into the corresponding bis-borinic ester allows for the direct and diastereoselective two-fold allyl transfer to aldehydes. This affords C - or C -symmetric stereotetrads containing a 1,4-diol moiety for natural product synthesis. The usefulness of our method was demonstrated with a short synthesis of the lignan (±)-neo-olivil.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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confidence: 99%

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A Versatile Bis‐Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols

et al. 2018

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“…Because the reagent preparation required the use of pyrophoric dialkylhaloboranes, its use has been limited. [15] For our purposes, we required a reagent that could be accessed on a large scale and exhibited predictable reactivity and stereoselectivity. As the isomeric purity and stability of allylboron reagents is critical to their synthetic utility, we decided to focus on pinacol boronate esters, which led us to bis-allylboronate 1 (Scheme 2).…”

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confidence: 99%

Ein vielseitiges Bisallylbor‐Reagenz für die stereoselektive Synthese von chiralen Diolen

et al. 2018

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Allylboration of Carbonyl Compounds

Lachance

Hall

2009

Organic Reactions

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Allylic boron compounds have gained a prominent status in organic synthesis for their ability to add with high stereoselectivity to carbonyl compounds such as aldehydes, making them a methodology of choice for the preparation of acetate and propionate units found in several classes of natural products. This remarkable reaction process was discovered in 1964, only to become popular in the 1980s. Using either the dialkylborane or boronate reagents, both the thermal uncatalyzed reaction and the more recent acid‐catalyzed procedures can provide homoallylic alcohol products in high enantioselectivity. The wide of range of possibilities for substitution on the reagent's allylic unit has led to the development of numerous reagents, and the residual alkene unit in the products confers to allylboration chemistry a unique versatility. This chapter presents an exhaustive survey of the useful reagents and their associated carbonyl substrates employed in organic synthesis. The mechanisms and parameters of the reaction are discussed, along with an overview of the different preparative methods for allylic boron reagents. The scope and limitations of these reagents in enantioselective additions, doubly diastereoselective additions, tandem reactions, and other variants is emphasized in the context of applications in natural product synthesis. The literature is covered through early 2006.

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Unprecedented stereoselectivity in a reaction of a novel diboron compound ? 1,6-bis(dialkylboryl)-2,4-hexadiene with carbonyl compounds

Cited by 6 publications

References 6 publications

A Versatile Bis‐Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols

A Versatile Bis‐Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols

Ein vielseitiges Bisallylbor‐Reagenz für die stereoselektive Synthese von chiralen Diolen

Allylboration of Carbonyl Compounds

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