1,3-Dipolar cycloaddition of diaryldiazomethanes across N-ethoxy-carbonyl-N-(2,2,2-trichloroethylidene)amine and reactivity of the resulting 2-azabutadienes towards thiolates and cyclic amides
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- 作者：Rodolphe Kinghata ; Gé ; rard Schmitta ; Kabula Ciamalaa ; Abderrahim Khatyra ; ; Michael Knorra ; michael.knorr@univ-fcomte.fr" class="auth_mail" title="E-mail the corresponding author ; Sandrine Jacquot-Rousseaua ; Yoann Rousselinb ; Marek M. Kubickib ; marek.kubicki@u-bourgogne.fr" class="auth_mail" title="E-mail the corresponding author
- 关键词：2-Azabutadienes ; Cycloaddition ; 1 ; 2 ; 4-Triazoline ; Azomethine ylides ; Thioether ; Macrocyclic complex ; Copper
- 刊名：Comptes Rendus Chimie
- 出版年：2016
- 出版时间：March 2016
- 年：2016
- 卷：19
- 期：3
- 页码：320-332
- 全文大小：992 K
文摘
1,3-dipolar cycloaddition of diaryldiazomethanes Ar2C
N2 across Cl3C–CHN–CO2Et 1 yields Δ3-1,2,4-triazolines 2. Thermolysis of 2 leads, via transient azomethine ylides 3, to diaryldichloroazabutadienes [Ar(Ar')CN–CHCCl2] 4. Treatment of 4a (Ar = Ar' = C6H5) and 4c (Ar = Ar' = p-ClC6H4) with NaSR in DMF yields 2-azabutadienes [Ar2CN–C(H)C(SR)2] 5. In contrast, nucleophilic attack of NaStBu on 4 affords azadienic dithioethers [Ar2CN–C(StBu)C(H)(StBu)] (7a Ar = C6H5; 7b Ar' = p-ClC6H4). The reaction of 4a with NaSEt conducted in neat EtSH produces [Ph2CN–C(H)(SEt)–CCl2H] 8, which after dehydrochloration by NaOMe and subsequent addition of NaSEt is converted to [Ph2CN–C(SEt)C(H)(SEt)] 7c. Upon the reaction of 4c with NaSiPr, the intermediate dithioether [(p-ClC6H4)2CN–CHC(SiPr)2] 5k is converted to tetrakisthioether [(p-iPrSC6H4)2CN–CHC(SiPr)2] 6. Treatment of 4a with the sodium salt of piperidine leads to [Ph2CN–CHC(NC5H10)2] 10. The coordination of 6 on CuBr affords the macrocyclic dinuclear Cu(I) complex 11. The crystal structures of 5i, 7a,b, 10 and 11 have been determined by X-ray diffraction.
N2 across Cl3C–CHN–CO2Et 1 yields Δ3-1,2,4-triazolines 2. Thermolysis of 2 leads, via transient azomethine ylides 3, to diaryldichloroazabutadienes [Ar(Ar')CN–CHCCl2] 4. Treatment of 4a (Ar = Ar' = C6H5) and 4c (Ar = Ar' = p-ClC6H4) with NaSR in DMF yields 2-azabutadienes [Ar2CN–C(H)C(SR)2] 5. In contrast, nucleophilic attack of NaStBu on 4 affords azadienic dithioethers [Ar2CN–C(StBu)C(H)(StBu)] (7a Ar = C6H5; 7b Ar' = p-ClC6H4). The reaction of 4a with NaSEt conducted in neat EtSH produces [Ph2CN–C(H)(SEt)–CCl2H] 8, which after dehydrochloration by NaOMe and subsequent addition of NaSEt is converted to [Ph2CN–C(SEt)C(H)(SEt)] 7c. Upon the reaction of 4c with NaSiPr, the intermediate dithioether [(p-ClC6H4)2CN–CHC(SiPr)2] 5k is converted to tetrakisthioether [(p-iPrSC6H4)2CN–CHC(SiPr)2] 6. Treatment of 4a with the sodium salt of piperidine leads to [Ph2CN–CHC(NC5H10)2] 10. The coordination of 6 on CuBr affords the macrocyclic dinuclear Cu(I) complex 11. The crystal structures of 5i, 7a,b, 10 and 11 have been determined by X-ray diffraction.