Pd-Catalyzed Arylation Reactions with Phenol Diazonium Salts: Application in the Synthesis of Diarylheptanoids

Schmidt, Bernd; Hölter, Frank; Kelling, Alexandra; Schilde, Uwe

doi:10.1021/jo2002787

Cited by 47 publications

(20 citation statements)

References 69 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[19] In particular, the strict exclusion of oxygen from the reaction vessel required for the SmI 2 reaction was not necessary,w hichm adet he Zn reagent an attractive and practical alternative. It was noted that the deoxygenation efficiency was solvent dependent (Table 1, entries 10 and 11 versus [14][15][16] and that the SET metal (Table 1, entries 8-10)h ad more influence on the yield than the leaving group (Table 1, entries 10-13).…”

Section: Resultsmentioning

confidence: 99%

“…[2a-c] The capricious reactivity of AR products under both acidic and basic conditions prompted us to explore an indirect arylation approachb ased on ar eductionoxidation process (Scheme 1b). Inspired by Schmidt's seminal work [15] on Heck-Matsuda [16] arylation of simple 6-substituted dihydropyran enol ethers with aryl diazonium salts for trans-selective synthesis of 2,6-disubstituted dihydropyrans, we envisioned that g-deoxygenation of AR products with migration of the double bond coupled with Heck-Matsuda arylation might provide av iable solution for the synthesis of trans-2-aryl-6-alkyl DHPOs VII (e.g., 3). Challenges in implementingt his strategy from am echanisticp oint of view include 1) chemo-and regioselective g-deoxygenation versus possible a-a nd g'-deoxygenation, and subsequent a-protonation versusp otential gprotonation that couldp roduce the thermodynamically morestable butu ndesired conjugate enone 4b and 2) unprecedented Heck-Matsudar eaction of d-keto cyclic enol ethers of type 4a.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues

et al. 2015

Chemistry A European J

View full text Add to dashboard Cite

Fully functionalized pyranuloses derived from Achmatowicz rearrangement (AR) are versatile building blocks in organic synthesis. However, access to trans-2,6-dihydropyrans from pyranuloses remains underexplored. Herein, we report a new two-step trans arylation of AR products to access 2,6-trans-dihydropyranones. This new trans-arylation method built on numerous plausible, but unsuccessful, direct arylation reactions, including Ferrier-type and Tsuji-Trost-type reactions, was finally enabled by an unprecedented, highly regioselective γ-deoxygenation of AR products by using Zn/HOAc and a diastereoselective Heck-Matsuda coupling. The synthetic utility of the reaction was demonstrated in the first asymmetric total synthesis of (-)-musellarins A-C and 12 analogues in 11-12 steps. The brevity and efficiency of our synthetic route permitted preparation of enantiomerically pure musellarins and analogues (>20 mg) for preliminary cytotoxicity evaluation, which led us to identify two analogues with three-to-six times greater potency than the musellarins as promising new leads.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues

et al. 2015

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The Heck-type cross-coupling reactions can also be performed with aryldiazonium salts [247, [273][274][275][276][277][278] (frequently called the Matsuda or Heck-Matsuda reaction), N-nitroso-N-arylacetamides [248], and hypervalent iodo compounds [250] at room temperature.…”

Section: The Leaving Groupsmentioning

confidence: 99%

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

Bräse¹,

Meijere²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

View full text Add to dashboard Cite

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.

show abstract

“…3 Using electrospray ionization mass spectrometry, the gas-phase reaction between piperazine and halobenzyl cations, formed by the dissociation of N-(halobenzyl)piperazines, has been investigated. No evidence for the formation of arylpentazoles was found.…”

mentioning

confidence: 99%

“…The experimental results are in accord 126 with a molecular Ni(I)/Ni(III) mechanism outlined in Scheme 4. 130 Ni(PR 3 127 Coupling of aryltrimethylammonium iodide salts with arylzinc reagents is catalysed by nickel tricyclohexylphosphine in a tetrahydrofuran-N-methyl pyrrolidine solvent.…”

mentioning

confidence: 99%

Nucleophilic Aromatic Substitution

Crampton

2014

Organic Reaction Mechanisms Series

View full text Add to dashboard Cite

Pd-Catalyzed Arylation Reactions with Phenol Diazonium Salts: Application in the Synthesis of Diarylheptanoids

Cited by 47 publications

References 69 publications

Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues

Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues

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

Nucleophilic Aromatic Substitution

Contact Info

Product

Resources

About