Total Synthesis of (−)-Secu’amamine A Exploiting Type II Anion Relay Chemistry

Han, Heeoon; Smith, Amos B.

doi:10.1021/acs.orglett.5b02018

Cited by 25 publications

(13 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Also, the sequence of intramolecular aza‐Michael addition–aldol addition–lactonization developed by Weinreb and co‐workers for the construction of secu′amamine A from a linear precursor should be mentioned at this point . Smith and co‐workers synthesized this alkaloid using anion relay chemistry . Another unique approach toward the bridged B/C/D ring system of 1 was recently reported by Snyder and co‐workers (Scheme ) .…”

Section: Total Synthesis Of Securinega Alkaloidssupporting

confidence: 57%

Securinega Alkaloids: Complex Structures, Potent Bioactivities, and Efficient Total Syntheses

Wehlauch

Gademann

2017

Asian J Org Chem

View full text Add to dashboard Cite

The Securinega alkaloids feature a compact tetracyclic structural framework and can be divided into four subclasses characterized by either a bridged [2.2.2]‐ or a [3.2.1]‐bicyclic core with two homologous series in each subclass. In the last two decades, many innovative strategies to chemically access the Securinega alkaloids have been developed. This Focus Review discusses the selected structures and syntheses of representative members of the Securinega alkaloids. Ring‐closing metathesis has enabled the syntheses of securinine and norsecurinine, and different cycloaddition approaches were key to the syntheses of nirurine and virosaines A and B. Virosine A was accessed through a Vilsmeier–Haack/Mannich reaction cascade. A bio‐inspired vinylogous Mannich reaction has enabled the synthesis of allosecurinine and this strategy has been extended by an intramolecular 1,6‐addition to obtain bubbialidine and secu′amamine E. A rearrangement process of the latter two alkaloids has furnished allonorsecurinine and allosecurinine, respectively. Finally, an expanded model for the biogenesis of the Securinega alkaloid subclasses is discussed.

show abstract

Section: Total Synthesis Of Securinega Alkaloidssupporting

confidence: 57%

Securinega Alkaloids: Complex Structures, Potent Bioactivities, and Efficient Total Syntheses

Wehlauch

Gademann

2017

Asian J Org Chem

View full text Add to dashboard Cite

show abstract

“…Secu'amamine A( 12)c onsists of an atypical aza-bicyclo-[3,3,1]-nonane core structure. [12] This unique 1,2-amine shift based framework presents interesting (bio)synthetic questions.E ven though there have been model studies hinting at ap otential 1,2-amine shift during the biosynthesis of this natural product, [13] its execution in ar eal system has been elusive because of the difficulty in accessing the C3-oxidized securinega derivative.H ence,d espite two previous elegant total syntheses of this natural product, [14,15] key questions regarding the biosynthetically relevant 1,2-amine shift have remained unanswered. Fluvirosaones A( 13)a nd B ( 14), pentacyclic securinega alkaloids recently isolated from Flueggea virosa,c onsist of ac yclopentenone Ering that is constructed by two carbon-carbon bond formations between the external three-carbon unit and the base securinega structure.…”

Section: Introductionmentioning

confidence: 99%

Biosynthetically Inspired Syntheses of Secu′amamine A and Fluvirosaones A and B

et al. 2020

View full text Add to dashboard Cite

Presented here is a concise synthesis of secu′amamine A, and fluvirosaones A and B from readily available allosecurinine and viroallosecurinine. The key C2‐enamine derivative of (viro)allosecurinine, the presumed biosynthetic precursors of these natural products, was accessed, for the first time, by a VO(acac)2‐mediated regioselective Polonovski reaction. Formal hydration and 1,2‐amine shift of this pluripotent enamine compound afforded secu′amamine A. Formal oxidative [3+2] cycloaddition reaction between this enamine and TMS‐substituted methallyl iodide reagent paved the way to the precursors of fluvirosaones A and B. The relative stereochemistry at the C2 position of these advanced intermediates governs the fate of 1,2‐amine shift leading to fluvirosaones A and B. The syntheses of potential biosynthetic precursors and investigations of their chemical reactivities have provided insights regarding the biogenesis of these natural products.

show abstract

“… 9 Over the past decade, we have reported extensive studies in the area of through-space ARC employing Brook rearrangements, which led to the evolution of types I and II ARC union tactics ( Scheme 1 ). 10 The potential of each of the ARC tactics has been demonstrated separately in a number of completed or ongoing synthetic ventures, including those on (+)-spongistatin 1 and 2, 11 (+)-spirastrellolide A and B, 12 (−)-secu’amamine A, 13 and most recently (−)-enigmazole A. 14 Herein, we illustrate the strategic value of both types I and II ARC union tactics with a total synthesis of (−)-mandelalide A ( 1 ).…”

mentioning

confidence: 99%

Total Synthesis of (−)-Mandelalide A Exploiting Anion Relay Chemistry (ARC): Identification of a Type II ARC/CuCN Cross-Coupling Protocol

et al. 2016

Self Cite

View full text Add to dashboard Cite

Anion relay chemistry (ARC), an effective, multicomponent union tactic, was successfully employed for the total synthesis of the highly cytotoxic marine macrolide (−)-mandelalide A (1). The northern hemisphere was constructed via a new type II ARC/CuCN cross-coupling tactic, while the southern hemisphere was secured via a highly efficient four-component type I ARC union. Importantly, the synthesis of 1 showcases ARC as a rapid, scalable coupling strategy for the union of simple readily available building blocks to access diverse complex molecular fragments with excellent stereochemical control.

show abstract

Total Synthesis of (−)-Secu’amamine A Exploiting Type II Anion Relay Chemistry

Cited by 25 publications

References 49 publications

Securinega Alkaloids: Complex Structures, Potent Bioactivities, and Efficient Total Syntheses

Securinega Alkaloids: Complex Structures, Potent Bioactivities, and Efficient Total Syntheses

Biosynthetically Inspired Syntheses of Secu′amamine A and Fluvirosaones A and B

Total Synthesis of (−)-Mandelalide A Exploiting Anion Relay Chemistry (ARC): Identification of a Type II ARC/CuCN Cross-Coupling Protocol

Contact Info

Product

Resources

About