A Powerful Chiral Phosphoric Acid Catalyst for Enantioselective Mukaiyama–Mannich Reactions

Zhou, Fengtao; Yamamoto, Hisashi

doi:10.1002/ange.201603929

Cited by 12 publications

(4 citation statements)

References 53 publications

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“…In the following years, Akiyama's group investigated the scopeo ft his reaction, giving rise to aw ide array of derivatives. [72] In spite of the high yields achieved with dinitrophenyl catalyst derivatives 133 and 134 (see Figure 5), the enantioselectivity was moderate at best and always lower than Akiyama's reportedr esults (see Scheme 45). [72] In spite of the high yields achieved with dinitrophenyl catalyst derivatives 133 and 134 (see Figure 5), the enantioselectivity was moderate at best and always lower than Akiyama's reportedr esults (see Scheme 45).…”

Section: Disulfonimide and Phosphoric Acid Catalystsmentioning

confidence: 83%

“…[71] Following Akiyama's work, Yamamoto and Zhou studied the same reactions in terms of the application of other chiral phosphorica cid derivatives as catalysts by modifying the aromatic substituents at the 3,3'-positions in the catalyst structure ( Figure 5). [72] In spite of the high yields achieved with dinitrophenyl catalyst derivatives 133 and 134 (see Figure 5), the enantioselectivity was moderate at best and always lower than Akiyama's reportedr esults (see Scheme 45). To increaset he enantioselectiv- In their ensuing work, Yamamoto and Zhou rendered the 2hydroxyphenyl moiety in aldimines unnecessaryi no rder to reach good enantioselectivities.…”

Section: Organocatalytic Mukaiyama-mannich Reactions 31 Disulfonimimentioning

confidence: 83%

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Development and Application of Asymmetric Organocatalytic Mukaiyama and Vinylogous Mukaiyama‐Type Reactions

Frías

Cieślik

Fraile

et al. 2018

Chemistry A European J

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Organocatalysis is a growing area that is benefiting from advances in many fields. Its implementation has begun in areas such as supramolecular chemistry, organic chemistry and natural product synthesis. While a considerable number of important publications in the field of organocatalytic Mukaiyama-type additions have been reported, they are yet to be fully covered in a review. Therefore, we would like to highlight the applications of various kinds of organocatalysts in Mukaiyama-type reactions, while also including the vinylogous Mukaiyama variation. Herein we describe and discuss the development and current state of the art of the organocatalytic Mukaiyama reaction, vinylogous Mukaiyama and related reactions.

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Section: Disulfonimide and Phosphoric Acid Catalystsmentioning

confidence: 83%

Section: Organocatalytic Mukaiyama-mannich Reactions 31 Disulfonimimentioning

confidence: 83%

Development and Application of Asymmetric Organocatalytic Mukaiyama and Vinylogous Mukaiyama‐Type Reactions

Frías

Cieślik

Fraile

et al. 2018

Chemistry A European J

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“… [64] It was previously shown that substrates lacking an OH group in the N−Ph moiety cannot be effectively activated by BINOL‐based chiral phosphoric acids 1 . In contrast, more acidic catalysts, such as N ‐triflylphosphoramides (Scheme 1d) and (trifluoromethyl)sulfonyl methanes (Scheme 1c), provide fast reactivity, good yields and excellent ee values [24,65] …”

Section: Resultsmentioning

confidence: 99%

“…In contrast, more acidic catalysts, such as Ntriflylphosphoramides (Scheme 1d) and (trifluoromethyl)sulfonyl methanes (Scheme 1c), provide fast reactivity, good yields and excellent ee values. [24,65] Given that the free acid 4 is prone to oxidation and hydrolysis, the reactive complex 14 was prepared in situ in a way avoiding the presence of free acid. First imine 13 is mixed with an ethereal solution of HCl (10 mol %) forming the iminium hydrochloride.…”

Section: First Reactivity Testsmentioning

confidence: 99%

Chiral Diselenophosphoric Acids for Ion Pair Catalysis: A Novel Approach to Enhance Both Proton Donating and Proton Accepting Properties

Eder,

Antonov,

Tupikina

et al. 2024

Chemistry A European J

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The activation of poorly reactive substrates via strong chiral acids is a central topic in asymmetric ion pair catalysis these days. Despite highly successful scaffolds such as N‐triflylphosphoramides, these catalysts either lack C2‐symmetry or provide multiple H‐bond acceptor sites, leading to lower ee values for certain reactions. We present BINOL‐based diselenophosphoric acids (DSA) as an extremely promising alternative. Using an intertwined approach of synthesis and NMR studies, we developed a synthetic approach to DSA with up to 98% NMR yield. The obtained acids provide both very high proton donor and proton acceptor properties, a bifunctionality, which is key to catalytic applications. Indeed, first reactivity test proved the much higher acidity of DSA and its ability to initiate Mukaiyama–Mannich reaction and protodesilylation of silyl ethers. Together with their C2‐symmetry, the single donor and single acceptor situation, the decreased tendency of self‐association, and the straightforward synthesis with potential 3,3’‐substitution, the DSA provide all features ideal for the further development of ion pair catalysis.

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Synthesis of β‐Naphthols and Naphthofuranones from ortho‐Alkynylarylketones via Sequential AgTFA‐Catalyzed Ketonization–Intramolecular Aldol Condensation: A Total Synthesis of Negundin A

et al. 2018

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As equential synthesis of b-naphthols and naphtho [2,3-b]furan-2(3H)-ones (naphthofuranones) has been developed using ortho-alkynylarylketonesa st he substrates. The AgTFA-catalyzed ketonization generated the corresponding 1,5-diketonei ntermediates in situ;t hese weref urther cyclized via aldol condensation under basic conditions to obtain b-naphthol products in moderate to good yields. For the synthesis of naphtho[2,3-b]furan-2(3H)-ones, an additional lactonization step was appliedt og ive ab road range of products in good yields. Moreover,t his methodh as also been utilized in the synthesis of natural product negundin A.Scheme1.The reported methodsf or the synthesis of b-naphthols. Scheme2.Our methodology for the synthesis of5min KOH (10.0 equiv), MeOH, 85 8C, 3min < 59 [c] 585 8C, 5min LiOH (10.0equiv), MeOH, 85 8C, 1h < 58 [c] 685 8C, 5min KO t Bu (10.0 equiv), MeOH, rt, 1h < 34 [c] 785 8C, 5min KO t Bu (10.0 equiv), t-BuOH, rt, 1h < 42 [c] 885 8C, 5min KO t Bu (10.0 equiv), THF,rt, 1h -[d] 985 8C, 5min NaO t Bu (10.0 equiv), MeOH, rt, 1h < 51 [c] 10 H 2 O( 1.0 equiv), rt, 15 min KOH (10.0 equiv), MeOH,8 58C, 3min 61 11 H 2 O( 1.0 equiv), rt, 15 min KOH (10.0 equiv), MeOH,r t, 25 min 62 [a] Yields of isolated products are reported. [b] Only 1,5-diketone was observed.[ c] Product containedi mpurities. [d] Complex mixture. [e] O/N = overnight. Scheme3.Substrate scope.Y ields of isolated products are reported. [a] Only the 1,5-diketone was observed;[b] the reaction in step 1w as carried out at 85 8C. Scheme4.Substrate scope expansion. Yields of isolatedproducts are reported. [a] The reaction in step 1w as stirred at room temperature overnight; [b] the reaction in step 1 [b] was stirreda troomtemperaturef or 6h. Scheme5.Reactionmonitoring of compound 1z-OH. Scheme6.Scope of substrate for the synthesis of naphtho[2,3-b]furan-2(3H)ones. Yields of isolated products are reported.[a] The reaction in step 1was carried out at 85 8C. Scheme7.To tal synthesis of negundin A. 1 HNMR (400 MHz, CDCl 3 ): d = 7.66 (d, 1H, J = 8.4 Hz), 7.38-7.32 (m, 2H), 7.26-7.22 (m, 2H), 7.17-7.14 (m, 2H), 7.07-7.05 (m, 2H), 5.06

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A Powerful Chiral Phosphoric Acid Catalyst for Enantioselective Mukaiyama–Mannich Reactions

Cited by 12 publications

References 53 publications

Development and Application of Asymmetric Organocatalytic Mukaiyama and Vinylogous Mukaiyama‐Type Reactions

Development and Application of Asymmetric Organocatalytic Mukaiyama and Vinylogous Mukaiyama‐Type Reactions

Chiral Diselenophosphoric Acids for Ion Pair Catalysis: A Novel Approach to Enhance Both Proton Donating and Proton Accepting Properties

Synthesis of β‐Naphthols and Naphthofuranones from ortho‐Alkynylarylketones via Sequential AgTFA‐Catalyzed Ketonization–Intramolecular Aldol Condensation: A Total Synthesis of Negundin A

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