Enantioselective Intramolecular Friedel−Crafts-Type α-Arylation of Aldehydes

Nicolaou, K. C.; Reingruber, Rüdiger; Šarlah, David; Bräse, Stefan

doi:10.1021/ja902682t

Cited by 29 publications

(20 citation statements)

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“…Moreover, the isomers formed from these reactions result from cyclization occurring at the more hindered carbon atom of the δ-aryl ring. This observed site selectivity is consistent with previous research by both MacMillan and Nicolaou on the α-arylation of aldehydes through organo-SOMO activation [18–21]. The preferential formation of these isomers will be discussed below.…”

Section: Resultssupporting

confidence: 90%

Mechanistic studies on the CAN-mediated intramolecular cyclization of δ-aryl-β-dicarbonyl compounds

Casey¹,

Sadasivam²,

Flowers³

2013

Beilstein J. Org. Chem.

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SummaryThe synthesis of 2-tetralones through the cyclization of δ-aryl-β-dicarbonyl substrates by using CAN is described. Appropriately functionalized aromatic substrates undergo intramolecular cyclizations generating 2-tetralone derivatives in moderate to good yields. DFT computational studies indicate that successful formation of 2-tetralones from δ-aryl-β-dicarbonyl radicals is dependent on the stability of the subsequent cyclohexadienyl radical intermediates. Furthermore, DFT computational studies were used to rationalize the observed site selectivity in the 2-tetralone products.

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Section: Resultssupporting

confidence: 90%

Mechanistic studies on the CAN-mediated intramolecular cyclization of δ-aryl-β-dicarbonyl compounds

Casey¹,

Sadasivam²,

Flowers³

2013

Beilstein J. Org. Chem.

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“…[7][8][9][10][11] Although various methodologies involving enamine and imine intermediates have been developed in organic synthesis, [12][13][14][15][16][17][18] single-electron oxidation of electron-rich enamine intermediates to trigger radical reactions is still rare despite the high activity of the in-situ-generated radical intermediates. [19][20][21][22] Recently, reactions through C-H [23][24][25][26][27] and C-C [28][29][30][31][32][33][34] cleavage have been powerful strategies for direct transformation of simple substrates. Thus, the combination of a single-electron transfer (SET) process with the generation of very active radical intermediates and C-H/C-C functionalization would potentially open the door to a new field of reaction discovery.…”

mentioning

confidence: 99%

Chemoselective Nitrosylation of Anilines and Alkynes via Fragmentary or Complete NO Incorporation

Pan

Lin

et al. 2018

Chem

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The cycloaddition reactions have been explored extensively and provided an efficient strategy for the synthesis of cyclic compounds. Traditionally, the reaction partners were in extenso incorporated into the cyclic products without fragmentation. From a different perspective, if certain fragmentations via chemical-bond cleavage are involved in this cycloaddition reaction, it would change the assembly sequence and enable more product diversity. Here, we report a chemoselective nitrosylation of anilines and alkynes through fragmentary or complete NO radical incorporation. The formation of multiple C-N bonds, an unexpected C-N bond, and N=O bond cleavage make this fragmentary cycloaddition reaction an efficient approach to 2,5-dihydrooxazoles, 1H-1,2,3-triazole 2-oxides or quinoxaline N-oxides. Facile operation in open-air, metal-free, and mild conditions renders this protocol particularly practical and attractive. A series of mechanistic studies and density functional theory calculations were also conducted, which help to explain the fragmentary or complete NO incorporation processes, broadening the field of new reaction discovery.

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“…To this end, and as shown in Scheme 10, we reacted (+)- 21 with readily available aldehydes 71 , 17 72 , and 73 (the latter two being commercially available) in the presence of BEt 3 to obtain coupling products 74 (66% yield), 76 (81% yield), and 78 (70% yield), respectively. The TBS group was removed from these products with TBAF to afford diols 75 (67% yield), 77 (64% yield), and 79 (77% yield), respectively.…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Total Synthesis of Antibiotic CJ-16,264, Synthesis and Biological Evaluation of Designed Analogues, and Discovery of Highly Potent and Simpler Antibacterial Agents

et al. 2017

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An improved and enantioselective total synthesis of antibiotic CJ-16,264 through a practical kinetic resolution and an iodolactonization reaction to form the iodo pyrrolizidinone fragment of the molecule is described. A series of racemic and enantiopure analogues of CJ-16,264 was designed and synthesized through the developed synthetic technologies and tested against drug-resistant bacterial strains. These studies led to interesting structure–activity relationships and the identification of a number of simpler, and yet equipotent, or even more potent, antibacterial agents than the natural product, thereby setting the foundation for further investigations in the quest for new anti-infective drugs.

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Enantioselective Intramolecular Friedel−Crafts-Type α-Arylation of Aldehydes

Cited by 29 publications

References 0 publications

Mechanistic studies on the CAN-mediated intramolecular cyclization of δ-aryl-β-dicarbonyl compounds

Mechanistic studies on the CAN-mediated intramolecular cyclization of δ-aryl-β-dicarbonyl compounds

Chemoselective Nitrosylation of Anilines and Alkynes via Fragmentary or Complete NO Incorporation

Enantioselective Total Synthesis of Antibiotic CJ-16,264, Synthesis and Biological Evaluation of Designed Analogues, and Discovery of Highly Potent and Simpler Antibacterial Agents

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