Enantioselective dialkylzinc-mediated alkynylation, arylation and alkenylation of carbonyl groups

Bauer, Tomasz

doi:10.1016/j.ccr.2015.03.025

Cited by 51 publications

(20 citation statements)

References 285 publications

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“…Among all of the attempts to construct the chiral diynols, the direct addition of a terminal 1,3-diyne to an aldehyde is the most efficient way. Lots of early works on the enantioselective alkynylation of aldehydes have proved the practicality of this method [10][11][12]. With this approach, the chiral center is formed along with the formation of the carbon-carbon bond; hence, the configuration of the diynols is controllable by using a proper catalyst.…”

Section: Resultsmentioning

confidence: 99%

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Total Synthesis of Chiral Falcarindiol Analogues Using BINOL-Promoted Alkyne Addition to Aldehydes

et al. 2016

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An enantioselective total synthesis of chiral falcarindiol analogues from buta-1,3-diyn-1-yltriisopropylsilane is reported. The key step in this synthesis is BINOL-promoted asymmetric diacetylene addition to aldehydes. The two chiral centers of the falcarindiol analogues can be produced by using the same kind of catalyst with high selectivity, and the final product can be obtained in only six steps.

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Section: Resultsmentioning

confidence: 99%

“…Buta-1,3-diyn-1-yltriisopropylsilane (4) was synthesized according to the literature with modifications [12]. Bromine (5 mL, 97.6 mmol, 0.9 eq.)…”

Section: Preparation Of Buta-13-diyn-1-yltriisopropylsilanementioning

confidence: 99%

Total Synthesis of Chiral Falcarindiol Analogues Using BINOL-Promoted Alkyne Addition to Aldehydes

et al. 2016

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“…The results of the calculations show that the statistically evolving chirality reaches higher levels than the sensitivity threshold of the asymmetric autocatalysis towards induction of chirality. These results should also be taken into account in mechanistic speculations of other organo-zinc mediated C-C bond coupling reactions [63].…”

Section: Discussionmentioning

confidence: 99%

Natural Abundance Isotopic Chirality in the Reagents of the Soai Reaction

2016

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Isotopic chirality influences sensitively the enantiomeric outcome of the Soai asymmetric autocatalysis. Therefore magnitude and eventual effects of isotopic chirality caused by natural abundance isotopic substitution (H, C, O, Zn) in the reagents of the Soai reaction were analyzed by combinatorics and probability calculations. Expectable enantiomeric excesses were calculated by the Pars-Mills equation. It has been found that the chiral isotopic species formed by substitution in the otherwise achiral reagents provide enantiomeric excess (e.e.) levels that are higher than the sensitivity threshold of the Soai autocatalysis towards chiral induction. Consequently, possible chiral induction exerted by these e.e. values should be taken into account in considerations regarding the molecular events and the mechanism of the chiral induction in the Soai reaction.

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“…The asymmetrica ddition of zinc alkynylide to carbonyl compoundsh as al ong history in asymmetric catalysis. One of the most popular classes of catalyst for this transformation is chiral titaniumcomplexes, [21] and numerous ligands have been developed to provides ynthetically valuable propargylic alcohols. Along these lines, the Ma group reported as ystem forp romoting the enantioselective alkynylation of fluorinated ketones, thereby producingt he corresponding products (15-20; Scheme 8).…”

Section: Use Of Preformed Alkynylides As Nucleophilesmentioning

confidence: 99%

“…Their catalytic system was based on a C 1 -symmetrical rhodium(III) complex that was ligatedw ith an NCN pincer ligand [27] (Scheme 13). [28] The scope of the reaction was broad with respect to the Scheme9.Enantioselective additiono fz inc alkynylide, catalyzed by achiral Schiff base (21).…”

Section: Direct Use Of Terminalalkynes As Pronucleophilesmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of α‐Trifluoromethylated Carbinols: A Case Study of Tertiary Propargylic Alcohols

2018

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Enantioenriched CF 3 -substituted tertiary alcohols have been applied in ab road range of chemical disciplines, including medicinal chemistry and agrochemistry. The widely prescribed anti-HIV pharmaceutical efavirenz is one particular example of the application of these chiral building blocks. Because the typical synthetic route to this small drug molecule involves the stoichiometric use of ac hiral promoter,s ignificant effort has been devoted to the development of catalytic alternatives for accessing this building block.I n this Focus Review,w es ummarize the catalytic asymmetric synthesis of CF 3 -substituted tertiary propargylic alcohols based on three retrosynthetic approaches, namely one trifluoromethylation approacha nd two building-block strategies.T he general challenges that are involved in the construction of aC F 3 -substituted tetrasubstituted stereogenic carbon speciesa re highlighted and possible future directions in the field are discussed.

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Enantioselective dialkylzinc-mediated alkynylation, arylation and alkenylation of carbonyl groups

Cited by 51 publications

References 285 publications

Total Synthesis of Chiral Falcarindiol Analogues Using BINOL-Promoted Alkyne Addition to Aldehydes

Total Synthesis of Chiral Falcarindiol Analogues Using BINOL-Promoted Alkyne Addition to Aldehydes

Natural Abundance Isotopic Chirality in the Reagents of the Soai Reaction

Catalytic Asymmetric Synthesis of α‐Trifluoromethylated Carbinols: A Case Study of Tertiary Propargylic Alcohols

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