Gold(<scp>i</scp>)-catalyzed access to neomerane skeletons

Tugny, Coralie; Khaled, Omar; Derat, Étienne; Goddard, Jean‐Philippe; Fensterbank, Louis

doi:10.1039/c7qo00360a

Cited by 6 publications

(12 citation statements)

References 39 publications

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“…The significance of this methodology was highlighted by the first total synthesis of 5-epivaleneomarin B 43 in 12 steps by employing Au(I)-catalyzed selective 1,2-acyl transfer as the key step (Scheme 11, eq 2). [139] In some cases, the intermediates 44 formed from Au(I)initiated 1,2-selective propargyl ester rearrangement can be trapped by enamides 45 in a [2 + 3] annulation process to generate functionalized azaspiro [4.4]nonane building blocks 46. The value of this one-flask tandem operation is emphasized in the total synthesis of Cephalotaxus alkaloids cephalezomine H 47 and cephalotoxine 48 by preparing a common spirointermediate 46 (Scheme 12).…”

Section: 2-selective Ester Shift Reactionsmentioning

confidence: 99%

Regio‐ and Site‐selective Molecular Rearrangements by Homogeneous Gold Catalysis

Praveen

2020

Asian J Org Chem

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Homogeneous gold catalysis for connection and disconnection of carbon-carbon (CÀ C) as well as carbonheteroatom (CÀ X) bond constitutes an important zone in molecular chemistry, since all new or existing organic synthesis relies on the transformation of these chemical bonds. Among the diaspora of molecular transformations, rearrangement and shift reactions occupy a special place in organic chemistry, as they enable the synthesis of molecules of increased complexity from simple precursors. However, the rearrangement in substrates possessing more than one potential reaction site produce more than one isomer and could result in regioselective issues. This challenge of selective synthesis of one regisomer over the other was fairly addressed by gold catalysis on various occasions. To this end, the prowess of homogeneous gold catalysis towards regioselective molecular rearrangement reactions and the contributing parameters are comprehensively reviewed. Also, synthetic applicability of regioselective rearrangements by gold catalysis in total and formal synthesis of several natural products was emphasized.This review also covers the emergence of gold catalyzed migratory/shift selective reactions and could be beneficial for synthetic and medicinal chemists.

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Section: 2-selective Ester Shift Reactionsmentioning

confidence: 99%

Regio‐ and Site‐selective Molecular Rearrangements by Homogeneous Gold Catalysis

Praveen

2020

Asian J Org Chem

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“… 499 Indeed, cyclobutane product 262 likely arises by [2 + 2] cycloaddition of an allenene formed in situ. 500 …”

Section: Construction Of 3-membered Rings Catalyzed By Goldmentioning

confidence: 99%

Gold-Catalyzed Synthesis of Small Rings

et al. 2020

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Three- and four-membered rings, widespread motifs in nature and medicinal chemistry, have fascinated chemists ever since their discovery. However, due to energetic considerations, small rings are often difficult to assemble. In this regard, homogeneous gold catalysis has emerged as a powerful tool to construct these highly strained carbocycles. This review aims to provide a comprehensive summary of all the major advances and discoveries made in the gold-catalyzed synthesis of cyclopropanes, cyclopropenes, cyclobutanes, cyclobutenes, and their corresponding heterocyclic or heterosubstituted analogs.

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“…We recently reported the access to neomerane sesquiterpenes skeleton, a 5,7,3‐fused ring, from a 1,7‐enynyl propargylic ester. The key step was a 1,2‐acyloxy migration/intramolecular cyclopropanation sequence (Scheme ) . We first investigated the synthesis of acetate propargyl precursor 28 necessary for the construction of the core of 5‐epi‐valeneomerin B starting from commercial available 6‐methyl‐5‐hepten‐2‐one.…”

Section: 2‐migrationmentioning

confidence: 99%

“…The key step was a 1,2-acyloxy migration/ intramolecular cyclopropanation sequence (Scheme 6). [25] We first investigated the synthesis of acetate propargyl precursor 28 necessary for the construction of the core of 5-epi- Intermolecular cyclopropanation could be judisciously used by Nevado and coworkers. [26] The gold(I)-catalyzed reaction of a propargyl acetate 31 with diene 32 can give rise to three types of adducts.…”

Section: Cyclopropanationmentioning

confidence: 99%

Gold‐Catalyzed Migration of Propargyl Acetate as an Entry into the Total Synthesis of Natural Products

Fensterbank

2018

Israel Journal of Chemistry

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Gold catalysis has emerged over the last two decades as a protocole of choice for the efficient and selective activation of a variety of organic functional groups. This has served to the total synthesis of natural products at several occasions. In this context, the gold‐catalyzed migration (1,2‐ or 1,3‐) of propargyl acetates has been particularly used. This review highlights these different synthetic developments which are presented according to the involved mechanisms.

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Gold(i)-catalyzed access to neomerane skeletons

Cited by 6 publications

References 39 publications

Regio‐ and Site‐selective Molecular Rearrangements by Homogeneous Gold Catalysis

Regio‐ and Site‐selective Molecular Rearrangements by Homogeneous Gold Catalysis

Gold-Catalyzed Synthesis of Small Rings

Gold‐Catalyzed Migration of Propargyl Acetate as an Entry into the Total Synthesis of Natural Products

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