Catalytic Enantioselective α‐Ketol Rearrangement

Wu, Hua; Andres, Rémi; Wang, Qian

doi:10.1002/anie.201812244

Cited by 33 publications

(8 citation statements)

References 49 publications

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“…Important examples include the industrial processes for the carbonylation of methanol to produce acetic acid catalyzed by rhodium (the Monsanto process), and iridium (the Cativa process) [13–15] . Additionally, the acyl migration process represents an essential tool for the construction of complex molecules [16–21] …”

Section: Methodsmentioning

confidence: 99%

Oxidative Coordination versus C³−C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes

Rivas

Alvarado-Monzón

González‐García

et al. 2021

Chemistry A European J

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Iridabicycles [Ir{κ3‐N,C,O‐(pyC(H)=C(C(O)Me)2}(Cl)(L−L)](L−L=cod (cod=1,5‐cyclooctadiene), 1 a; bipy (bipy=2,2’‐bipyridine), 1 b) have been obtained by oxidative coordination of 3‐(pyridine‐2‐yl‐methylene)pentane‐2,4‐dione L1, to the complexes [{Ir(μ‐Cl)(cod)}2] and [{Ir(μ‐Cl)(coe)2}2] (coe=cis‐cyclooctene), the latter in the presence of bipy. Remarkably, cleavage of the C3−C(O)Me bond of L1 has instead been achieved in the reaction with [Ir(Cl)(dmb)2] (dmb=2,3‐dimethylbutadiene), yielding a compound formulated as [Ir{κ2‐N,C‐(pyC(H)C(C(O)Me))}(CO)(μ‐Cl)(Me)]2, 2. Treatment of dimer 2 with DMSO or PMe3 produced the complexes[Ir{κ2‐N,C‐(pyC(H)C(C(O)Me)}(CO)Cl(Me)L] (L=DMSO, 3 a; PMe3, 3 b). Plausible mechanisms for the reactions leading to complexes 1 and 2 are proposed by means of DFT calculations.

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Section: Methodsmentioning

confidence: 99%

Oxidative Coordination versus C³−C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes

Rivas

Alvarado-Monzón

González‐García

et al. 2021

Chemistry A European J

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“…The α-ketol rearrangement, also called acyloin rearrangement, transforms the α-hydroxy aldehydes/ketones to their constitutional isomers via a 1,2-alkyl(aryl) migration (Scheme a). − The reaction takes place reversibly under acidic, basic, or thermal conditions leading to the thermodynamically more stable isomer. It has been exploited in total synthesis and structural modification of natural products and is involved in the biosynthesis of several classes of natural products.…”

Section: 2-shift In Domino Processesmentioning

confidence: 99%

Natural Product Synthesis Enabled by Domino Processes Incorporating a 1,2-Rearrangement Step

Delayre

Wang

2021

ACS Cent. Sci.

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The art of natural product total synthesis is closely associated with two major determinants: the development/application of novel chemical reactions and the innovation in strategic use of classic organic reactions. While purposely seeking/applying a new synthetic methodology allowing nonconventional bond disconnections could shorten the synthetic route, the development of domino processes composed of a series of well-established reactions could also lead to a concise, practical, and aesthetically appealing synthesis. As an important class of textbook reactions, the 1,2-anionotropic rearrangements discovered at the dawn of modern organic chemistry have important bearings not only on chemical synthesis but also on the conceptual breakthroughs in the field. In its basic form, the 1,2-shift affords nothing but a constitutional isomer of the starting material and is therefore not a complexity-generating transformation. However, such a simple 1,2-shift could in fact change the molecular topology if the precursor is cleverly designed. More dramatically, it can metamorphosize the structure of the substrate when it is combined with other transformations in a domino sequence. In this Outlook, we highlight recent examples of natural product synthesis featuring a key domino process incorporating a 1,2-anionotropic rearrangement. Specifically, domino reactions integrating Wagner−Meerwein, pinacol, α-ketol, α-aminoketone, α-iminol, or benzilic acid rearrangements will be discussed.

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“…In a similar investigation except with copper(II) as the metal and β-hydroxy-α-diketone 6 as the substrate, the catalyst containing the chiral bisoxazoline ligand ( S , S )- 8 led to the α-ketol rearrangement product 7 in 70% yield and 68% ee ( Figure 3 ) [ 5 ]. The study further demonstrated the effectiveness of the catalyst for a series of analogues of 6 bearing various replacements for the phenyl group, often proceeding with greater than 80% ee.…”

Section: Reviewmentioning

confidence: 99%

α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

Benz¹,

Murkin²

2021

Beilstein J. Org. Chem.

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In the presence of a suitable acid or base, α-hydroxyaldehydes, ketones, and imines can undergo isomerization that features the 1,2-shift of an alkyl or aryl group. In the process, the hydroxy group is converted to a carbonyl and the aldehyde/ketone or imine is converted to an alcohol or amine. Such α-ketol/α-iminol rearrangements are used in a wide variety of synthetic applications including asymmetric synthesis, tandem reactions, and the total synthesis and biosynthesis of natural products. This review explores the use of α-ketol rearrangements in these contexts over the past two decades.

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Catalytic Enantioselective α‐Ketol Rearrangement

Cited by 33 publications

References 49 publications

Oxidative Coordination versus C³−C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes

Oxidative Coordination versus C³−C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes

Natural Product Synthesis Enabled by Domino Processes Incorporating a 1,2-Rearrangement Step

α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

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Catalytic Enantioselective α‐Ketol Rearrangement

Cited by 33 publications

References 49 publications

Oxidative Coordination versus C3−C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes

Oxidative Coordination versus C3−C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes

Natural Product Synthesis Enabled by Domino Processes Incorporating a 1,2-Rearrangement Step

α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

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Product

Resources

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Oxidative Coordination versus C³−C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes

Oxidative Coordination versus C³−C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes