Asymmetric Synthesis of Axially Chiral Natural Products

Yang, He; Tang, Wenjun

doi:10.1002/9783527825172.ch7

“…While helically chiral molecules are relatively well-established in catalysis and nanoscience, 3,4 they are relatively rare in the realm of alkaloids and in particular alkaloid of such low molecular weight as sclerotioloid A (1). [5][6][7][8] Intrigued by these structural questions, we targeted sclerotioloid A's total synthesis.Terminal acetylides are a reasonably common motifs in particular fungal secondary metabolites. 9Sclerotioloid A (1), however, represents the first and only natural isolate containing an N-propargyl system.…”

mentioning

confidence: 99%

“…While helically chiral molecules are relatively well-established in catalysis and nanoscience, 3,4 they are relatively rare in the realm of alkaloids and in particular alkaloid of such low molecular weight as sclerotioloid A (1). [5][6][7][8] Intrigued by these structural questions, we targeted sclerotioloid A's total synthesis.…”

mentioning

confidence: 99%

Total Synthesis of Sclerotioloid A

Siitonen

¹

2023

Preprint

0

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A CommonC₂‐Symmetric 2,2’‐Biphenol Building Block and its Application in the Synthesis of (+)‐di‐epi‐Gonytolide A

Greb

¹

,

Drennhaus

²

,

Klischan

³

et al. 2023

Chemistry A European J

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A variety of biaryl polyketides exhibit remarkable bioactivities. However, their synthetic accessibility is often challenging. Herein, the enantioselective preparation and synthetic application of an axially chiral 2,2'-biphenol building block is outlined that represents a common motif of these intriguing natural products. Based on the highly regioselective and scalable bromination of a phenol precursor, a coupling process by Lipshutz cuprate oxidation was developed. A copper-mediated deracemization strategy proved to be superior to derivatization or kinetic resolution approaches. Key steps in the overall building block synthesis were rationalized through DFT studies. Utilizing the 2,2'-biphenol, a highly diastereoselective five step synthesis of formerly unknown (+)-di-epi-gonytolide A was developed, thus showcasing the building block's general potential for the synthesis of natural products and their derivatives. En route, the first enantioselective construction of a chromone dimer intermediate was established.

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Atroposelective Synthesis of Axially Chiral Styrenes Connecting an Axially Chiral Naphthyl-indole Moiety Using Chiral Phosphoric Acid Catalysis

Woldegiorgis

¹

,

Gu

²

,

Lin

³

2023

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The organocatalytic asymmetric reactions of C2-unsubstituted racemic naphthyl-indoles with orthoalkynylnaphthols were employed to synthesize axially chiral styrenes connected to an axially chiral naphthyl-indole unit. Utilizing chiral phosphoric acid as the catalyst, these axially chiral styrenes were prepared in good yields (up to 96%) and excellent stereoselectivity (up to >99.9% ee, >20:1 dr, and >99:1 E/Z) in mild conditions. Moreover, further synthetic transformations were achieved with high yields and excellent stereocontrol.

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Asymmetric Synthesis of Axially Chiral Natural Products

Cited by 4 publications

References 86 publications

Total Synthesis of Sclerotioloid A

Total Synthesis of Sclerotioloid A

A CommonC₂‐Symmetric 2,2’‐Biphenol Building Block and its Application in the Synthesis of (+)‐di‐epi‐Gonytolide A

Atroposelective Synthesis of Axially Chiral Styrenes Connecting an Axially Chiral Naphthyl-indole Moiety Using Chiral Phosphoric Acid Catalysis

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Asymmetric Synthesis of Axially Chiral Natural Products

Cited by 4 publications

References 86 publications

Total Synthesis of Sclerotioloid A

Total Synthesis of Sclerotioloid A

A CommonC2‐Symmetric 2,2’‐Biphenol Building Block and its Application in the Synthesis of (+)‐di‐epi‐Gonytolide A

Atroposelective Synthesis of Axially Chiral Styrenes Connecting an Axially Chiral Naphthyl-indole Moiety Using Chiral Phosphoric Acid Catalysis

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A CommonC₂‐Symmetric 2,2’‐Biphenol Building Block and its Application in the Synthesis of (+)‐di‐epi‐Gonytolide A