Copper‐Catalyzed Aerobic Oxidative Cyclization Cascade to Construct Bridged Skeletons: Total Synthesis of (−)‐Suaveoline

Tan, Qiuyuan; Zhao, Yang; Jiang, Dan; Cheng, Yuegang; Yang, Jing; Xi, Song; Zhang, Min

doi:10.1002/ange.201902155

Cited by 10 publications

(3 citation statements)

References 101 publications

(24 reference statements)

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“…Synthetic access to these (pseudo-)natural compounds was pioneered by Cook and co-workers, who have accomplished very elegant total synthesis of several indole alkaloids with this structural feature by using Dieckmann condensation to construct the N-bridged framework [13][14][15][16] . Besides, efficient strategies also include biomimetic synthesis and olefin metathesis by the Martin group 17,18 , a [5 + 2] cycloaddition/ring enlargement by the Gaich group 19,20 , and other methods [21][22][23] . However, despite these advances, most of the existing methods require tediously long steps including functional-group pre-installations and transformations, harsh reaction conditions, and complicated operations.…”

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confidence: 99%

“…Moreover, only sporadic examples that disclosed the synthesis of chiral azabicyclo [3.3.1]nonane compounds have been available so far (Fig. 1b), which utterly relied on utilizing chiral auxiliary 24 or employing chiral starting materials [14][15][16][17][18][19][20][21][22][23] , respectively. To the best of our knowledge, the catalytic asymmetric protocol for constructing such ring systems has never been reported to date, which remains a tremendous challenge and long-standing assignment in modern synthetic chemistry.…”

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confidence: 99%

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Asymmetric synthesis of N-bridged [3.3.1] ring systems by phosphonium salt/Lewis acid relay catalysis

Tan

Shen

et al. 2022

Nat Commun

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Optically pure pseudo-natural products (PNPs), particularly exemplified by azabicyclo[3.3.1]nonane molecules and their analogs provide an attractive platform for structure−activity relationship studies, and also lead new compound discovery in drug development. However, there are currently no examples of guiding catalytic asymmetric strategies available to construct such important PN-scaffolds, thus limiting their broad use. Here, we report a general and modular method for constructing these pseudo-natural N-bridged [3.3.1] ring systems via cascade process by bifunctional phosphonium salt/Lewis acid relay catalysis. A wide variety of substrates bearing an assortment of functional groups (59 examples) are compatible with this protocol. Other features include a [3 + 2] cyclization/ring-opening/Friedel-Crafts cascade pathway, excellent reactivities and stereoselectivities, easily available starting materials, step economy and scalability. The obtained enantioenriched products showed potential of preliminary anticancer activities. Insights gained from our studies are expected to advance general efforts towards the catalytic synthesis of challenging even unprecedented chiral PNPs, offering new opportunities for bioactive small-molecule discovery.

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confidence: 99%

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confidence: 99%

Asymmetric synthesis of N-bridged [3.3.1] ring systems by phosphonium salt/Lewis acid relay catalysis

Tan

Shen

et al. 2022

Nat Commun

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“…Zhang reported a Cu(II) catalyzed intramolecular cascade reaction of aerobic C−H oxidation/ring opening of cyclopropanol to construct a azabicyclo[3.3.1] nonane skeleton using inexpensive chiral starting materials (amino acids) in air, ultimately achieving the synergistic total synthesis of (−)‐sulviolin (Scheme 57). [85] In the conversion, CuCl 2 catalyzes the initial C−H oxidation and subsequent ring opening cyclization steps of cyclopropanol.…”

Section: Formation Of Heterocycles Via Aerobic Oxidation Of C−h Bondmentioning

confidence: 99%

Recent Advances in Aerobic Oxidative of C−H Bond by Molecular Oxygen Focus on Heterocycles

Zhang

Wang

Lucan

et al. 2023

Chemistry A European J

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Aerobic oxidative cross‐coupling represents one of the most straightforward and atom‐economic methods for construction of C−C and C−X (X=N, O, S, or P) bonds using air as a sustainable external oxidant. The oxidative coupling of C−H bonds in heterocyclic compounds can effectively increase their molecular complexity by introducing new functional groups through C−H bond activation, or by formation of new heterocyclic structures through cascade construction of two or more sequential chemical bonds. This is very useful as it can increase the potential applications of these structures in natural products, pharmaceuticals, agricultural chemicals, and functional materials. This is a representative overview of recent progress since 2010 on green oxidative coupling reactions of C−H bond using O2 or air as internal oxidant focus on Heterocycles. It aims to provide a platform for expanding the scope and utility of air as green oxidant, together with a brief discussion on research into the mechanisms behind it.

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Asymmetric Total Synthesis of Sarpagine and Koumine Alkaloids

et al. 2021

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We report here aconcise,collective,and asymmetric total synthesis of sarpagine alkaloids and biogenetically related koumine alkaloids,w hichs tructurally feature ar igid cage scaffold, with l-tryptophan as the starting material. Tw ok ey bridged skeleton-forming reactions,namely tandem sequential oxidative cyclopropanol ring-opening cyclization and ketone a-allenylation, ensure concurrent assembly of the caged sarpagine scaffold and installation of requisite derivative handles.W ith ac ommon caged intermediate as the branch point, by taking advantage of ketone and allene groups therein, total synthesis of five sarpagine alkaloids (affinisine,n ormacusine B, trinervine,N a -methyl-16-epipericyclivine,a nd vellosimine) with various substituents and three koumine alkaloids (koumine,k oumimine,a nd N-demethylkoumine)w ith more complex cage scaffolds has been accomplished.

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Copper‐Catalyzed Aerobic Oxidative Cyclization Cascade to Construct Bridged Skeletons: Total Synthesis of (−)‐Suaveoline

Cited by 10 publications

References 101 publications

Asymmetric synthesis of N-bridged [3.3.1] ring systems by phosphonium salt/Lewis acid relay catalysis

Asymmetric synthesis of N-bridged [3.3.1] ring systems by phosphonium salt/Lewis acid relay catalysis

Recent Advances in Aerobic Oxidative of C−H Bond by Molecular Oxygen Focus on Heterocycles

Asymmetric Total Synthesis of Sarpagine and Koumine Alkaloids

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