Terminating catalytic asymmetric Heck cyclizations by stereoselective intramolecular capture of η3-allylpalladium intermediates: total synthesis of (−)-spirotryprostatin B and three stereoisomers

Overman, Larry E.; Rosen, Mark D.

doi:10.1016/j.tet.2010.05.048

Cited by 39 publications

(9 citation statements)

References 52 publications

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“…The intermediate palladium-allyl species was intercepted by the amide nitrogen under the same reaction conditions to generate the spirotryprostatin framework (Scheme 15b). 33 A total synthesis of tryprostatin B, a bioactive prenylindole alkaloid related to the spirotriprostatins, involved an initial domino process carried out in an aqueous buffer containing magnesium nitrate that involved the intramolecular N-alkylation of the DKP nitrogen of cyclo-(L-Trp-L-Pro) 51 with the iminium cation generated in the C-3 alkylation of the pendant indole ring by prenyl bromide. This reaction gave a mixture of the pentacyclic compound 52 and the target tryprostatin B (54).…”

Section: Methods Involving Alkylation At the Dkp Nitrogenmentioning

confidence: 99%

Privileged scaffolds in synthesis: 2,5-piperazinediones as templates for the preparation of structurally diverse heterocycles

et al. 2012

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Section: Methods Involving Alkylation At the Dkp Nitrogenmentioning

confidence: 99%

Privileged scaffolds in synthesis: 2,5-piperazinediones as templates for the preparation of structurally diverse heterocycles

et al. 2012

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“…It has been reported that N-hydroxymethyl dicarboximides can be hydrolyzed under basic conditions to furnish the corresponding unsubstituted dicarboximides. [24][25][26][27][28][29] Ensuing attempts to hydrolyze N-hydroxymethyl…”

Section: Scheme 1 General Conditions Derivatization (In Conjunction Withmentioning

confidence: 99%

“…In an effort to limit such unwanted hydrolysis, a selection of tertiary amine bases were screened (to be used under non-aqueous conditions). 28,29 Reactions employing either N-methylmorpholine (NMM), 1,4diazabicyclo[2.2.2]octane (DABCO), triethylamine (TEA) or N,N-diisopropylethylamine (DIPEA) (in order of increasing base strength) resulted in only the partial conversion of N-hydroxymethyl NRB 29 to NRB (12%, 9%, 16%, 81%, respectively, rt, 24 h; according to achiral RP-HPLC of the reaction mixture). Conversely, the reaction proceeded to completion within 15 minutes in the presence of strongly basic, non-nucleophilic 1,8diazabicyclo [5.4.0]undec-7-ene (DBU) (pKa 12).…”

Section: Scheme 1 General Conditions Derivatization (In Conjunction Withmentioning

confidence: 99%

Separation, characterisation and biological evaluation of the individual isomers of the rat selective toxicant norbormide – isolated using a chemical derivatization strategy

Jay-Smith¹,

Wang²,

Al‐Kassas³

et al. 2021

Arkivoc

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Norbormide[5-(α-hydroxy-α-2-pyridylbenzyl)-7-(α-2-pyridylbenzylidene)-5-norbornene-2,3-dicarboximide] (NRB, 1), an existing but infrequently used rodenticide, is known to be uniquely toxic to rats but relatively harmless to other rodents/mammals. However, as an acute vasoactive, NRB has a rapid onset of action, often leading to sub-lethal uptake/bait shyness. Recently, it was brought to our attention that baits containing two independently sourced batches of NRB (which differed noticeably in their stereochemical composition) displayed markedly different palatability/efficacy profiles in rats. Accordingly, with a view to independently evaluating the individual isomers of NRB in rats by means of a palatability and efficacy bait trial, this research describes the isolation of the individual isomers of endo-NRB (Y, V, W and U) from the parent mixture, by means of a chemical derivatization strategy.

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“…This methodology has been utilized by Overman et al in their elegant total syntheses of various natural products (Section 8.6), such as quadrigemine C [416], psycholeine [416], and other molecules of this type [417].…”

Section: Enantioselective Heck-type Reactionsmentioning

confidence: 99%

“…8.72Ligand-induced asymmetric Heck coupling of 2,3-dihydrofuran[411][412][413][414][415][416][417][418][419][420][421].…”

mentioning

confidence: 99%

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

Bräse¹,

Meijere²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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The carbopalladation of an alkene by an organylpalladium halide is the essential step in one of the major contemporary metal-catalyzed C-C coupling reactions. About 45 years ago, a Japanese and an American group almost simultaneously designed and executed palladium-mediated coupling reactions of aryl and alkenyl halides with alkenes [1]. In subsequent investigations, Richard Heck and his group developed this reaction into a catalytic transformation and started to demonstrate its usefulness as well as its rather broad scope. The real push to utilize this powerful C-C-bondforming process, however, started only around the mid-1980s, and by now, an impressive number of publications have established the meanwhile so-called Heck reaction [2] 1) as an indispensable method in Organic Synthesis [3][4][5][6][7]. The universal recognition of the importance of the Heck reaction and the Negishi as well as the Suzuki coupling eventually won the Nobel Prize for Richard Heck along with Ei-ichi Negishi and Akira Suzuki in 2010. The applications of the Heck reaction range from the preparation of -functionalized and unfunctionalized -hydrocarbons, novel polymers, and dyes to new advanced enantioselective syntheses of natural products and biologically active nonnatural compounds. The more or less simultaneous developments of mechanistically related variants, namely, the Kumada, Suzuki, Stille, Hiyama, and Negishi coupling reactions (Chapters 12, 2, 3, 4, and 15, respectively) of metallated alkenes and arenes with aryl and alkenyl halides or the metal-catalyzed formation and cycloisomerization of enynes have drawn profit from the improvement of and mechanistic insights into the Heck reaction. This, of course, applies vice versa as well. Using only a catalytic amount of a palladium(0) complex or a precursor to a palladium species, the Heck reaction can bring about unprecedented structural changes, particularly when conducted intramolecularly. The full potential of this palladium-catalyzed process is still being further explored as demonstrated by a total of over 7000 publications in the past 40 years by 1) The alkynylation of aryl and alkenyl halides, frequently also considered as Heck reactions, is described in Chapter 6.

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Terminating catalytic asymmetric Heck cyclizations by stereoselective intramolecular capture of η3-allylpalladium intermediates: total synthesis of (−)-spirotryprostatin B and three stereoisomers

Cited by 39 publications

References 52 publications

Privileged scaffolds in synthesis: 2,5-piperazinediones as templates for the preparation of structurally diverse heterocycles

Privileged scaffolds in synthesis: 2,5-piperazinediones as templates for the preparation of structurally diverse heterocycles

Separation, characterisation and biological evaluation of the individual isomers of the rat selective toxicant norbormide – isolated using a chemical derivatization strategy

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

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