Mo−Au Combo Catalysis for Rapid 1,3-Rearrangement of Propargyl Alcohols into α,β-Unsaturated Carbonyl Compounds

Egi, Masahiro; Yamaguchi, Yoshiko; Fujiwara, N.; Akai, Shuji

doi:10.1021/ol800596c

Cited by 143 publications

(70 citation statements)

References 22 publications

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“…Since the enone substructure of 27 is part of a 12‐membered ring and hence any cycloalkyne precursor necessarily strained, the macrocyclization by RCAM as well as the rearrangement chemistry are deemed fairly challenging. In fact, additional intelligence had suggested that an approach to dehydrocurvularin via a Meyer–Schuster rearrangement might be stereo‐unselective 50. Therefore we opted for the redox route shown in Scheme , which commenced with formylation of the commercial aryl bromide 28 followed by addition of propynylmagnesium bromide and protection of the resulting alcohol with a TBS group.…”

Section: Resultsmentioning

confidence: 99%

Increasing the Structural Span of Alkyne Metathesis

Persich

Llaveria

Lhermet

et al. 2013

Chemistry A European J

105

116

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A new generation of alkyne metathesis catalysts, which are distinguished by high activity and an exquisite functional group tolerance, allows the scope of this transformation to be extended beyond its traditional range. They accept substrates that were previously found problematic or unreactive, such as propargyl alcohol derivatives, electron-deficient and electron-rich acetylenes of various types, and even terminal alkynes. Moreover, post-metathetic transformations other than semi-reduction increase the structural portfolio, as witnessed by the synthesis of a annulated phenol derivative via ring-closing alkyne metathesis (RCAM) followed by a transannular gold-catalyzed Conia-ene reaction. Further examples encompass a post-metathetic transannular ketone-alkyne cyclization with formation of a trisubstituted furan, a ruthenium-catalyzed redox isomerization, and a Meyer-Schuster rearrangement/oxa-Michael cascade. These reaction modes fueled model studies toward salicylate macrolides, furanocembranolides, and the cytotoxic macrolides acutiphycin and enigmazole A; moreover, they served as the key design elements of concise total syntheses of dehydrocurvularin (27) and the antibiotic agent A26771B (36).

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Section: Resultsmentioning

confidence: 99%

Increasing the Structural Span of Alkyne Metathesis

Persich

Llaveria

Lhermet

et al. 2013

Chemistry A European J

105

116

View full text Add to dashboard Cite

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“…1‐(Oct‐1‐yn‐1‐yl)cyclohexanol (3j): 2g Pale yellow oil. IR (film): $\tilde {\nu}$ = 3392, 2932, 2858, 1698, 1448, 1379, 1341, 1332, 1258, 1179, 1132, 1066, 1057, 964, 904 cm –1 .…”

Section: Methodsmentioning

confidence: 99%

Alkynylation of Aldehydes and Ketones Using the Bu₄NOH/H₂O/DMSO Catalytic Composition: A Wide‐Scope Methodology

et al. 2014

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The Favorsky reaction of a wide range of aldehydes and ketones with alkynes has been implemented under mild conditions (5–20 °C). Using a Bu4NOH/H2O/DMSO catalytic system, propargylic alcohols are formed cleanly in 39–93 % (mostly 72–93 %) yields and with ca. 100 % selectivity. The method is suitable for aliphatic, aromatic, and heteroaromatic aldehydes and ketones, and for aliphatic, aromatic, and functionalized acetylenes. Thus, this represents the most general and efficient protocol to achieve the Favorsky reaction.

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“…In 2008, Akai's group [26] described a very efficient Meyer-Schuster rearrangement by the combined use of MoO 2 (acac) 2 [27] reported another practical synthesis of linear α-iodo/ bromo-β-unsaturated aldehydes/ketones directly from propargylic alcohols (Scheme 18). In this reaction, two metals complexes, MoO 2 (acac) 2 and PPh 3 AuNTf 2 catalyzed this reaction collaboratively.…”

Section: Gold/lewis Acid Bimetallic Catalysismentioning

confidence: 99%

Recent Advances of the Combination of Au/Acid Catalysis

et al. 2014

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Recently, homogeneous gold catalysis has attracted tremendous attention and has also been widely used in multistep synthesis. The current reaction methodology starts from the gold activation of unsaturated carbon bond and subsequent nucleophilic attack. The combination of a gold catalyst with another acid catalyst, including Brønsted acid and Lewis acid, is possible to bring two distinctive catalytic systems together and deliver unprecedented new reactions. More essentially, it avoids the purification of unstable intermediates and improves the step and atom economy. Here, the recent progress in the Au/Acid combined catalysis is reviewed, including the scope of reactions, mechanism and synthetic applications. REVIEW 938 www.cjc.wiley-vch.de

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Mo−Au Combo Catalysis for Rapid 1,3-Rearrangement of Propargyl Alcohols into α,β-Unsaturated Carbonyl Compounds

Cited by 143 publications

References 22 publications

Increasing the Structural Span of Alkyne Metathesis

Increasing the Structural Span of Alkyne Metathesis

Alkynylation of Aldehydes and Ketones Using the Bu₄NOH/H₂O/DMSO Catalytic Composition: A Wide‐Scope Methodology

Recent Advances of the Combination of Au/Acid Catalysis

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Mo−Au Combo Catalysis for Rapid 1,3-Rearrangement of Propargyl Alcohols into α,β-Unsaturated Carbonyl Compounds

Cited by 143 publications

References 22 publications

Increasing the Structural Span of Alkyne Metathesis

Increasing the Structural Span of Alkyne Metathesis

Alkynylation of Aldehydes and Ketones Using the Bu4NOH/H2O/DMSO Catalytic Composition: A Wide‐Scope Methodology

Recent Advances of the Combination of Au/Acid Catalysis

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Alkynylation of Aldehydes and Ketones Using the Bu₄NOH/H₂O/DMSO Catalytic Composition: A Wide‐Scope Methodology