Generation of <i>N</i>-Acyliminium Ions via Intramolecular Conjugate Addition Reactions:  A Strategy for the Total Synthesis of Nakadomarin A

Nilson, Mark G.; Funk, Raymond L.

doi:10.1021/ol061463y

Cited by 40 publications

(15 citation statements)

References 27 publications

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“…The synthesis of ent ‐nakadomarin A by the Kerr group (Scheme ) made use of their innovative cycloaddition methodology for the generation of highly substituted pyrrolidines ( 9 + 10 + 11 → 8 → 7 ), and ultimately yielded the alkaloid in a sequence that was more concise than those of their predecessors 4. In addition to these completed syntheses, several approaches toward this popular target have been disclosed by other groups,5 with those of the Funk5f and Zhai5g groups both being notable for the construction of the ABCD tetracycle by very short, stereocontrolled sequences; concise syntheses of nakadomarin A are surely being developed in these laboratories. In light of all the excellent previous work, the spectacular synthesis recently disclosed by Jakubec, Cockfield, and Dixon,6 which no doubt benefited substantially from this prior art, raises the bar in terms of strategic elegance and step economy7 for nakadomarin A.…”

Section: Methodsmentioning

confidence: 99%

Concise Synthesis of (−)‐Nakadomarin A

Martin

Vanderwal

2010

Angew Chem Int Ed

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Section: Methodsmentioning

confidence: 99%

Concise Synthesis of (−)‐Nakadomarin A

Martin

Vanderwal

2010

Angew Chem Int Ed

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“…Based on some interesting reactions like Michael addition, cascade cyclization, Ring Closing Metathesis and acyliminium ion cyclization, they synthesized the target efficiently in 21 steps (Scheme ). InCl 3 catalyzed cascade reaction was performed on 47 (prepared from compound 46 and 46 a following Knoevenagel condensation reaction, with selectively E isomer) to afford the tetracyclic core 48 in excellent yield. Later, attention was paid to the formation of F ring system based on RCM strategy.…”

Section: Synthetic Approaches For the Total Synthesismentioning

confidence: 99%

Recent Developments on the Total Synthesis of Nakadomarin A

Jana

Mekonnen

2018

ChemistrySelect

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Nakadomarin A is an alkaloid belongs to manzamine family having architecturally complex structure and exhibits promising biological activities. To accomplish this target molecule, few novel synthetic strategies have been developed by eminent synthetic chemists. This review will highlight the important and improved synthetic approaches for the total synthesis of natural as well as unnatural isomers of nakadomarin A. All synthetic strategies have been enlightened from the cluster of literatures to develop a more elegant strategy for the molecule in future.

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“…25 The analogous tert-butyl carbamate of 36 gave the tert-butyl analogue of 39 in the same yield and with the same trans/cis diastereoselectivity (Scheme 16). 26 The use of vinyl sulfide 40 as an olefinic component in the three-component coupling reaction of the N-acyliminium ion 11 and silicon nucleophiles gave the products 41 in 56-75% yields (Scheme 17 An N-acyliminium ion was selectively generated in the polymer-supported dipeptide 42 by oxidation of the N-silylmethyl group with ceric ammonium nitrate in methanol. The resulting N-methoxymethyl carbamate reacted with allyltrimethylsilane in the presence of boron trifluoride-diethyl ether complex to give the polymer-supported allylated product 43.…”

Section: Scheme 13mentioning

confidence: 99%

Intermolecular Addition Reactions of N-Acyliminium Ions (Part I)

Yazici¹,

Pyne²

2009

Synthesis

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I n t e r m o l e c u l a r A d d i t i o n R e a c t i o n s o f N -A c y l i m i n i u m I o n s ( P a r t I )Abstract: This review highlights the advances in the literature up to July 2008 on the intermolecular reactions of acyclic and cyclic Nacyliminium ions. This is an update of an earlier review in 2000 on this topic and does not include intramolecular addition reactions to N-acyliminium ions which was recently reviewed. This review is presented in two parts, with the first part dealing with acyclic and pyrrolidinone-based N-acyliminium ions. Part II continues with other five-membered heterocyclic derivatives and higher systems. IntroductionThis review highlights the advances in the literature up to July 2008 on the intermolecular reactions of acyclic and cyclic N-acyliminium ions. This is an update of an earlier review in 2000 2 on this topic and does not include intramolecular addition reactions to N-acyliminium ions which was recently reviewed. 3 A review article on addition reactions to related, but less reactive, N-acylimines has also been recently published. 4The highly reactive nature of N-acyliminium ions require that they are generated in situ usually in the presence of the other reactive, electron-rich, nucleophilic partner (NuY, Y = metal, SiR 3 , SnR 3-, etc.). In general these intermediates are generated from more stable and isolatable asubstituted N-acylamines of the type 1 by treatment with a Lewis acid or sometimes a protic acid (Scheme 1). The reaction of 2 with a nucleophilic species (NuY) then gives a-substituted N-acylamine 3. Compounds 1-3 can be acyclic systems or R 1 and R 2 , R 2 and R 3 , R 1 and R 3 can be taken together to form part of a ring system as shown in the general structures 4, 5, and 6.Compounds like 1 (X = OH and NHCO 2 R) are most likely formed in situ from the Lewis acid promoted threecomponent, one-pot coupling reactions of carbamates, aldehydes (or acetals) and silyl nucleophiles or electronrich aromatic nucleophiles (Scheme 2). 5,6N-Acyliminium ions like 11 can also be generated in dichloromethane solution, in the absence of nucleophiles, by the electrochemical oxidation of N-trimethylsilylmethyl carbamates like 10 (Scheme 3). These intermediates have been characterised spectroscopically and were subDownloaded by: Florida International University. Copyrighted material.

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Generation of N-Acyliminium Ions via Intramolecular Conjugate Addition Reactions: A Strategy for the Total Synthesis of Nakadomarin A

Abstract: [reaction: see text] The rapid construction of the tetracyclic core ring system of nakadomarin A via a tandem enecarbamate Michael addition/N-acyliminium ion cyclization is described.

Cited by 40 publications

References 27 publications

Concise Synthesis of (−)‐Nakadomarin A

Concise Synthesis of (−)‐Nakadomarin A

Recent Developments on the Total Synthesis of Nakadomarin A

Intermolecular Addition Reactions of N-Acyliminium Ions (Part I)

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