Facile Synthesis of a Family of H<sub>8</sub>BINOL-Amine Compounds and Catalytic Asymmetric Arylzinc Addition to Aldehydes

DeBerardinis, Albert M.; Turlington, Mark; Ko, Jason; Sole, Laura; Pu, Lin

doi:10.1021/jo1000516

Cited by 48 publications

(37 citation statements)

References 52 publications

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“…Compound 9 was employed in the addition of heteroarylzinc reagent to an aldehyde with good enantioselectivity by Pu in 2010 (Scheme 11). 27,28 Scheme 11. Asymmetric arylzinc addition to aldehydes catalysed by 9.…”

Section: Binols 33′-disubstituted By Acyclic Functional Groupsmentioning

confidence: 99%

BINOLs modified at 3, 3′-positions: chemists’ preferred choice in asymmetric catalysis

Li¹,

Liu²,

Wu³

2015

Arkivoc

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This article provides a general overview of the most relevant topics in the applications of BINOL modified at the 3 and 3′-positions in asymmetric catalysis. A brief introduction to the chiral BINOL backbone so modified is given. A selection of the most outstanding uses of the catalysts according to the functional groups at the 3,3′-positions of BINOL backbones such as 3,3′-disubstituents of BINOLs, phosphoric acid derivatives and phosphoramidites is then presented. This review aims to introduce the latest developments of this active field, including the literature since 2008.

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Section: Binols 33′-disubstituted By Acyclic Functional Groupsmentioning

confidence: 99%

BINOLs modified at 3, 3′-positions: chemists’ preferred choice in asymmetric catalysis

Li¹,

Liu²,

Wu³

2015

Arkivoc

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“…[12] We investigated the use of (S)-1 to promote the reaction of vinyl iodides with aldehydes in the presence of ZnEt 2 . We were pleased to find that using 10 mol % of (S)-1 can catalyze the reaction of Scheme 1.…”

mentioning

confidence: 99%

“…[12] Among these compounds, (S)-1 was found to catalyze the highly enantioselective arylzinc addition to aldehydes in a number of cases. [12] We investigated the use of (S)-1 to promote the reaction of vinyl iodides with aldehydes in the presence of ZnEt 2 .…”

mentioning

confidence: 99%

Activation of Vinyl Iodides for the Highly Enantioselective Addition to Aldehydes

DeBerardinis

Turlington

2011

Angew Chem Int Ed

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Grignard and organolithium reagents can be directly prepared from organohalides and are of great importance in organic synthesis. However, the high reactivity of these reagents makes it difficult to develop enantioselective catalysts for their nucleophilic addition to carbonyls to generate chiral alcohols. [1][2][3] In the past two decades, the use of organozinc reagents in asymmetric catalysis has been studied extensively. [4,5] Organozinc reagents are generally less reactive and more tolerant of functional groups than Grignard and organolithium reagents. These characteristics have allowed the rapid development of enantioselective catalysts for the asymmetric organozinc addition to carbonyls. Among these studies, several highly enantioselective catalysts were found for the asymmetric addition of vinylzinc compounds to carbonyls to generate chiral allylic alcohols. [6][7][8][9] In these reports, the vinylzinc reagents were prepared by using methods such as the hydrozirconation [6] or hydroboration [7] of alkynes with subsequent transmetallation, vinyl boronic acids or esters, [8] and the nickel-catalyzed addition of ZnMe 2 to alkynes.[9] The hydrozirconation and hydroboration of terminal alkynes generate alkenylzirconiums and alkenylboranes, respectively, which upon treatment with alkylzinc reagents can form the corresponding alkenylzinc reagents. These reagents in the presence of chiral ligands have been shown to be very useful for the asymmetric addition to carbonyls. [6, 7] However, the use of the hydrozirconation and hydroboration of terminal alkynes has limitations. For example, these methods cannot be applied to make cycloalkenylzinc reagents and only terminal alkynes are used in most cases. Preparation of vinylzinc reagents directly from vinyl halides would avoid these limitations. There is no report yet on the catalytic asymmetric reaction of carbonyl compounds with vinylzinc reagents that are prepared directly from vinyl halides without using the magnesium or lithium reagents, which are less tolerant of functional groups.[10] In 2004, Knochel and co-workers demonstrated that aryl iodides can be converted into arylzinc compounds by using ZniPr 2 , [11] but it was not known whether this strategy was applicable to vinyl iodides. Herein, we report the discovery of a highly enantioselective catalyst for the reaction of vinyl iodides with aldehydes through the direct conversion of vinyl iodides into vinylzinc reagents in the presence of ZnEt 2 . This method allows the synthesis of substituted and functionalized allylic alcohols with high enantiomeric purity under very mild reaction conditions. We first examined the reaction of a vinyl iodide, (E)-1-iodo-1-phenyl-1-pentene, with c-C 6 H 11 CHO in the presence of ZnEt 2 (Scheme 1). This led to the formation of the corresponding allylic alcohol in only a 17 % yield. The reactions of other vinyl iodides with aldehydes were also tested and these reactions normally gave low yields of product except for a few cases. These results indicate that the vinylzinc rea...

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“…In 1999, Koichi Mikami et al developed an HPLC-CD-based system 18 , which allows the simultaneous detection of the CD signal Δε, the absorption ε, and their ratio g = Δε/ε.…”

Section: Circular Dichroism (Cd)mentioning

confidence: 99%

“…Synthesis and Characterization of (R)-6-6. 18 Under nitrogen, (R) 5',6,6',7,7',8,, (R)- 6-5 (25 mmol, 7.4 g), was dissolved in THF (300 mL). The solution was cooled to 0 º C, and NaH (62.8 mmol, 60% in mineral oil, 2.52 g) was added in small portions.…”

Section: Synthesis and Characterization Of Compoundsmentioning

confidence: 99%

Enantioselective Fluorescent Sensors for Chiral Alpha-Hydroxycarboxylic Acids, Amino Acid derivatives and Diamines

Sheng

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A series of enantioselective fluorescent sensors based on chiral 1,1'-bi-2-naphathol (BINOL) was designed and developed for the recognition of chiral α-hydroxycarboxylic acids, amino acid derivatives and diamines.A new concept with the use of a pseudoenantiomeric fluorescent sensor pair for A BINOL-amino alcohol enantiomeric pair is discovered to be able to conduct both enantioselective and diastereoselective fluorescent discrimination of the four stereoisomers of threonine derivatives. This is the first example that one enantiomeric sensor pair can be used to recognize four stereoisomers of chiral substrates containing iii two chiral centers.A BINOL-trifluoroacetyl compound is discovered to exhibit high sensitivity at one emission wavelength and high enantioselectivity at another when treated with a chiral diamine. By using this fluorescent sensor it was demonstrated for the first time that both the concentration and enantiomeric composition of a chiral substrate can be determined simultaneously with one fluorescent measurement.These discoveries represent important progress in the field of enantioselective fluorescent sensors and have fundamental significance for the potential application of fluorescence in chiral catalyst screening.

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Facile Synthesis of a Family of H₈BINOL-Amine Compounds and Catalytic Asymmetric Arylzinc Addition to Aldehydes

Cited by 48 publications

References 52 publications

BINOLs modified at 3, 3′-positions: chemists’ preferred choice in asymmetric catalysis

BINOLs modified at 3, 3′-positions: chemists’ preferred choice in asymmetric catalysis

Activation of Vinyl Iodides for the Highly Enantioselective Addition to Aldehydes

Enantioselective Fluorescent Sensors for Chiral Alpha-Hydroxycarboxylic Acids, Amino Acid derivatives and Diamines

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Facile Synthesis of a Family of H8BINOL-Amine Compounds and Catalytic Asymmetric Arylzinc Addition to Aldehydes

Cited by 48 publications

References 52 publications

BINOLs modified at 3, 3′-positions: chemists’ preferred choice in asymmetric catalysis

BINOLs modified at 3, 3′-positions: chemists’ preferred choice in asymmetric catalysis

Activation of Vinyl Iodides for the Highly Enantioselective Addition to Aldehydes

Enantioselective Fluorescent Sensors for Chiral Alpha-Hydroxycarboxylic Acids, Amino Acid derivatives and Diamines

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Facile Synthesis of a Family of H₈BINOL-Amine Compounds and Catalytic Asymmetric Arylzinc Addition to Aldehydes