Stereoselective Synthesis of 7‐(<i>E</i>)‐Arylidene‐2‐chloro‐6‐azabicyclo[3.2.1]octanes <i>via</i> Aluminum Chloride‐Promoted Cyclization/Chlorination of Six‐Membered Ring 3‐Enynamides

Yeh, Ming Chang P.; Chang, Yi Mei; Lin, Hsin Hui

doi:10.1002/adsc.201700271

Cited by 7 publications

(1 citation statement)

References 47 publications

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“…By contrast, the anodic chlorination of P3HT smoothly proceeded in the presence of a Lewis acid (Table 1, entry 2, 3) because of the suppression of the anodic oxidation of Cl − ions. 39 In small-molecular chemistry, AlCl 3 is known to function as both a Lewis acid and a nucleophilic chlorine source; 41,42 thus, we speculated that the chlorination could proceed without the addition of Et 4 NCl. We performed the anodic chlorination of P3HT using AlCl 3 as a Lewis acid, a supporting electrolyte, and a chlorine source (Table 1, entry 4).…”

Section: Resultsmentioning

confidence: 99%

Post-Functionalization of Aromatic C–H Bonds at the Main Chains of π-Conjugated Polymers via Anodic Chlorination Facilitated by Lewis Acids

et al. 2021

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C−H functionalization of π-conjugated polymers is a straightforward approach to changing their optoelectronic properties and aggregation behavior; however, the functionalization methodologies and applicable precursor polymers remain limited. Here, we demonstrated the electrochemical aromatic C−H chlorination of π-conjugated polymers using aluminum chloride (AlCl 3 ). AlCl 3 facilitated the anodic oxidation of precursor polymers in acetonitrile (MeCN), and the AlCl 3 /MeCN system exhibited greater oxidation tolerance than other electrolyte systems. Given these discoveries, we achieved anodic chlorination of poly(3hexylthiophene) with high current efficiency and expanded applicable precursor polymers such as poly(p-phenylene) derivatives and poly(9,9-dioctylfluorene) (PFO). The regioselectivity of the chlorination of PFO was clarified on the basis of detailed nuclear magnetic resonance studies of the chlorinated PFO. The optoelectronic properties and aggregation behavior of the precursor polymers were substantially changed after chlorination.

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Section: Resultsmentioning

confidence: 99%

Post-Functionalization of Aromatic C–H Bonds at the Main Chains of π-Conjugated Polymers via Anodic Chlorination Facilitated by Lewis Acids

et al. 2021

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Organocatalytic Enantioselective Conia‐Ene‐Type Carbocyclization of Ynamide Cyclohexanones: Regiodivergent Synthesis of Morphans and Normorphans

Sun

Tan

et al. 2019

Angewandte Chemie

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Described herein is an organocatalytic enantioselective desymmetrizing cycloisomerization of arylsulfonyl‐protected ynamide cyclohexanones, representing the first metal‐free asymmetric Conia‐ene‐type carbocyclization. This method allows the highly efficient and atom‐economical construction of a range of valuable morphans with wide substrate scope and excellent enantioselectivity (up to 97 % ee). In addition, such a cycloisomerization of alkylsulfonyl‐protected ynamide cyclohexanones can lead to the divergent synthesis of normorphans as the main products with high enantioselectivity (up to 90 % ee). Moreover, theoretical calculations are employed to elucidate the origins of regioselectivity and enantioselectivity.

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Expedient Synthesis of Bridged Bicyclic Nitrogen Scaffolds via Orthogonal Tandem Catalysis

et al. 2021

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Bridged nitrogen bicyclic skeletons have been accessed via unprecedented site‐ and diastereoselective orthogonal tandem catalysis from readily accessible reactants in a step economic manner. Directed Pd‐catalyzed γ‐C(sp3)‐H olefination of aminocyclohexane with gem‐dibromoalkenes, followed by a consecutive intramolecular Cu‐catalyzed amidation of the 1‐bromo‐1‐alkenylated product delivers the interesting normorphan skeleton. The tandem protocol can be applied on substituted aminocyclohexanes and aminoheterocycles, easily providing access to the corresponding substituted, aza‐ and oxa‐analogues. The Cu catalyst of the Ullmann‐Goldberg reaction additionally avoids off‐cycle Pd catalyst scavenging by alkenylated reaction product. The picolinamide directing group stabilizes the enamine of the 7‐alkylidenenormorphan, allowing further product post functionalizations. Without Cu catalyst, regio‐ and diastereoselective Pd‐catalyzed γ‐C(sp3)‐H olefination is achieved.

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Stereoselective Synthesis of 7‐(E)‐Arylidene‐2‐chloro‐6‐azabicyclo[3.2.1]octanes via Aluminum Chloride‐Promoted Cyclization/Chlorination of Six‐Membered Ring 3‐Enynamides

Cited by 7 publications

References 47 publications

Post-Functionalization of Aromatic C–H Bonds at the Main Chains of π-Conjugated Polymers via Anodic Chlorination Facilitated by Lewis Acids

Post-Functionalization of Aromatic C–H Bonds at the Main Chains of π-Conjugated Polymers via Anodic Chlorination Facilitated by Lewis Acids

Organocatalytic Enantioselective Conia‐Ene‐Type Carbocyclization of Ynamide Cyclohexanones: Regiodivergent Synthesis of Morphans and Normorphans

Expedient Synthesis of Bridged Bicyclic Nitrogen Scaffolds via Orthogonal Tandem Catalysis

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