Regio‐ and Stereoselective Syntheses of 7‐Oxabicyclo[2.2.1]heptanes <i>via</i> a Gold(I)‐Catalyzed Cycloisomerization of Alkynediols: Asymmetric Total Synthesis of Farnesiferol C

Gu, Yueqing; Zhang, Pengpeng; Fu, Junkai; Liu, Song; Lan, Yu; Gong, Jianxian; Yang, Zhen

doi:10.1002/adsc.201600218

Cited by 17 publications

(6 citation statements)

References 48 publications

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“…351 More highly substituted cyclopentanones with only one stereogenic center also did not undergo highly stereoselective additions (Scheme 206). 352 In the case of a cyclopentanone fused to an aromatic ring, stereoselectivity depended upon the nucleophile (Scheme 207). 353 Addition of vinylmagnesium bromide occurred with high diastereoselectivity, presumably because the diastereotopic faces were significantly differentiated due to the ring fusion.…”

Section: Steric Approach Control and Stereoselectivitymentioning

confidence: 99%

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

et al. 2020

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This review describes the additions of allylmagnesium reagents to carbonyl compounds and to imines, focusing on the differences in reactivity between allylmagnesium halides and other Grignard reagents. In many cases, allylmagnesium reagents either react with low stereoselectivity when other Grignard reagents react with high selectivity, or allylmagnesium reagents react with the opposite stereoselectivity. This review collects hundreds of examples, discusses the origins of stereoselectivities or the lack of stereoselectivity, and evaluates why selectivity may not occur and when it will likely occur. CONTENTS 4.2.5. Additions to β-Substituted Aldehydes 4.2.6. Additions to Aldehydes with Distant Chelating Groups 4.3. Additions to Cyclic Ketones 4.3.1. Alkoxy-Substituted Cyclic Ketones 4.3.2. Additions to Alkoxy-Substituted Five-Membered-Ring Ketones 4.3.3. Additions to Alkoxy-Substituted Four-Membered-Ring Ketones 4.4. Additions of Allylmagnesium Halides to Cyclic Hemiacetals 5. Diastereoselectivity of Reactions of Allylmagnesium Reagents with Carbonyl Compounds by Felkin−Anh Control 5.1. Felkin−Anh Stereoselectivity 5.2. Additions to α-Chiral Acyclic Ketones 5.3. Additions to Chiral Exocyclic Ketones and Aldehydes 5.4. Additions of Allylmagnesium Halides to Chiral Cyclic Ketones Controlled by Felkin−Anh Selectivity 5.5. Additions of Allylmagnesium Halides to Chiral Acyclic Aldehydes 6. Diastereoselectivity of Reactions with Carbonyl Compounds by Steric Approach Control 6.1. Steric Approach Control and Stereoselectivity

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Section: Steric Approach Control and Stereoselectivitymentioning

confidence: 99%

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

et al. 2020

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“…Indeed, this method is applied as a key step in the total synthesis of natural product, Farnesiferol C 64 (Scheme 13). [171] Another evidence for the utility of this gold‐catalyzed methodology came in 2015, in which the asymmetric formal total synthesis of (+)‐cortistatins was accomplished [172] . In another disclosure, the total synthesis of Orientalol‐F is realized through the Au(I)‐catalyzed domino cycloisomerization of alkynediol as key step for the formation of corresponding seven membered bicyclic intermediate [173] .…”

Section: Cyclization Of Oxygen Tethered C−c Multiple Bondsmentioning

confidence: 99%

Cycloisomerization of π‐Coupled Heteroatom Nucleophiles by Gold Catalysis: En Route to Regiochemically Defined Heterocycles

Praveen

2021

The Chemical Record

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Since the dawn of millennium, catalytic gold chemistry is at the forefront to set off diverse organic reactions via unique activation of π‐bonded molecules. Within this purview, cycloisomerization of heteroatom nucleophiles linked to a π‐system is one of the well recognized chemistry for the construction of numerous heterocyclic cores. Though the rudimentary aspects of this transformation are reviewed by several groups in different timeline, a holistic view on regiochemistry of such reactions went largely overlooked. Hence, this account emphasizes the gold catalyzed regioselective cycloisomerization of structurally distinctive π‐connected hetero‐nucleophiles leading to different heterocycles documented in the last two decades. From an application perspective, this account also highlights those methodologies which find a role in the total synthesis of natural products. Wherever appropriate, mechanistic details and contributing factors for selectivity are also discussed.

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“…In 2016, this type of gold(I)‐catalyzed cycloisomerization was also used for the asymmetric total synthesis of Farnesiferol C . As summarized in Scheme , key step was the construction of the 7‐oxabicyclo[2.2.1]heptane core 76 from diol 75 , using a gold‐catalyzed cascade sequence consisting of heterocyclization and 1,2‐migration.…”

Section: Applications In Total Synthesesmentioning

confidence: 99%

[1, 2]‐Migration Reactions Catalyzed by Gold Complexes and their Applications in Total Synthesis

Holzschneider

Kirsch

2018

Israel Journal of Chemistry

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The area of cascade reactions, initiated by the transition metal‐catalyzed activation of π‐systems and coupled with a 1,2‐migration step is of considerable interest in current organic chemistry research. In this article, recent advances in the field are highlighted, focusing on gold as the activating π‐acid. Cascade reactions with 1,2‐shifts of alkyl groups as migrating agents are mainly presented, but also selected 1,2‐aryl migrations and miscellaneous examples are depicted. With the reactions discussed, molecules of high structural complexity become readily accessible. Examples are shown where the reactions were used as the key steps of total synthesis endeavours.

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Regio‐ and Stereoselective Syntheses of 7‐Oxabicyclo[2.2.1]heptanes via a Gold(I)‐Catalyzed Cycloisomerization of Alkynediols: Asymmetric Total Synthesis of Farnesiferol C

Cited by 17 publications

References 48 publications

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

Cycloisomerization of π‐Coupled Heteroatom Nucleophiles by Gold Catalysis: En Route to Regiochemically Defined Heterocycles

[1, 2]‐Migration Reactions Catalyzed by Gold Complexes and their Applications in Total Synthesis

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