2016
DOI: 10.1002/anie.201603649
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Chiral Allenes via Alkynylogous Mukaiyama Aldol Reaction

Abstract: Herein we describe the development of a catalytic enantioselective alkynylogous Mukaiyama aldol reaction. The reaction is catalyzed by a newly designed chiral disulfonimide and delivers chiral allenoates in high yields and with excellent regio-, diastereo-, and enantioselectivity. Our process tolerates a broad range of aldehydes in combination with diverse alkynyl-substituted ketene acetals. The reaction products can be readily derivatized to furnish a variety of highly substituted enantiomerically enriched bu… Show more

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Cited by 149 publications
(62 citation statements)
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“…General Information. 1 H NMR, 13 C NMR, and 19 F NMR spectra were recorded in CDCl 3 using a 300 MHz NMR spectrometer ( 1 H at 300 MHz, 13 C at 75 MHz, 19 F at 282 MHz). Mass spectra (MS) and high-resolution mass spectra (HRMS) were carried out using electron impact ionization (EI) or electron spray ionization (ESI).…”
Section: Methodsmentioning
confidence: 99%
See 1 more Smart Citation
“…General Information. 1 H NMR, 13 C NMR, and 19 F NMR spectra were recorded in CDCl 3 using a 300 MHz NMR spectrometer ( 1 H at 300 MHz, 13 C at 75 MHz, 19 F at 282 MHz). Mass spectra (MS) and high-resolution mass spectra (HRMS) were carried out using electron impact ionization (EI) or electron spray ionization (ESI).…”
Section: Methodsmentioning
confidence: 99%
“…Catalytic enantioselective syntheses are always the most atom-economic and efficient method in asymmetric synthesis. Recently, transition metal-catalyzed enantioselective constructions of the axial chirality of allenes from 2-bromo-1,3-butadienes (path a), [12] racemic propargylic carbonates (path b), [13] stereo-defined enol triflates (path c), [14] conjugated enynes (path d), [15] and ketenes (path e), [16] etc., [17] have been developed; in addition, Maruoka and List et al applied the nucleophilic 1,2-addition of allenyl anions with aromatic imines or aldehydes (path f); [18,19] Feng et al developed the chiral Lewis acid-catalyzed rearrangement of propargylic cyclic enol ethers (path g) or conjugate addition of malonate with stereo-defined 1-aryl-1-en-3-ynes (path h); [20,21] These strategies show a great potential with very promising diastereoselectivities in some cases (Scheme 1A). On the other hand, racemic 2,3-allenol derivatives have successfully been applied for the generation of optically active allenes with a central or axial chirality under the catalysis of a palladium catalyst via the "allene-asymmerization" strategy with different chiral ligands (Scheme 1B, eqs.…”
Section: Introductionmentioning
confidence: 99%
“…Several traditional approaches utilize common chemical transformations, such as [3,3] and [2,3] sigmatropic rearrangements, S N 2′ displacements, and reductive transposition of chiral propargyl precursors to form enantiomerically enriched allenes. More recent methods have employed traditional catalytic asymmetric organocatalytic processes, such as a Mannich reaction, an alkynylogous Mukaiyama aldol reaction, or a three‐step sequence including a Petasis reaction . Furthermore, metal‐catalyzed asymmetric allene syntheses have been developed based on transformations of achiral dienes, terminal alkynes, or vinyl triflates .…”
Section: Figurementioning
confidence: 99%
“…32 Organocatalytic methods have been developed recently, 3336 such as an enantioselective alleno-Mannich reaction employing phase-transfer catalysis 35 and an enantioselective alkynylogous Mukaiyama aldol reaction using a chiral phosphoric acid catalyst. 36 While significant advances have been made, the development of broadly useful and convergent strategies to synthesize enantioenriched chiral allenes from achiral precursors remains a significant challenge.…”
Section: Introductionmentioning
confidence: 99%