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2.1.3.1 Reactions with a CH-Acid Component

DOI: 10.1055/sos-SD-211-00020

Shaabani, A.; Sarvary, A.; Shaabani, S.Science of Synthesis: Multicomponent Reactions, (2014255.

The preparation of annulated 4H-pyrans 3 based on the nucleophilic addition of isocyanides to dialkyl acetylenedicarboxylates in the presence of various annular CH-acids has been reported; see also Section 1.2.3.3.1.4. The formation of these heterocycles can be rationalized by the nucleophilic addition of isocyanides to dialkyl acetylenedicarboxylates and subsequent protonation of the 1:1 adduct 1 by CH-acids. Addition of CH-acid anions to the positively charged ions forms ketenimines 2, which, after tautomerization and cyclization under the reaction conditions, result in the formation of annulated 4H-pyrans 3 (Scheme 1). Cyclic 1,3-dicarbonyl compounds and related compounds such as 3-hydroxy-1H-phenalen-1-one,[‌6‌] 2,5-dihydroxybenzo-1,4-quinone, 2-hydroxynaphtho-1,4-quinone,[‌7‌] indene-1,3(2H)-dione,[‌8‌] 5,5-dimethylcyclohexane-1,3-dione,[‌9‌] cyclohexane-1,3-dione,[‌9‌] cyclopentane-1,3-dione,[‌9‌] 3-methylcyclopentane-1,2,4-trione,[‌10‌] 4-hydroxy-6-methyl-2H-pyran-2-one,[‌11‌] 4-hydroxy-2H-1-benzopyran-2-one,[‌12‌] furan-2,4(3H,5H)-dione,[‌13‌] and 2-hydroxycyclohepta-2,4,6-trien-1-one (α-tropolone)[‌14‌] have been employed. In addition, hetero-analogues of 1,3-dicarbonyl compounds such as isoxazol-4(5H)-one 4[‌15‌] and 1H-pyrazol-5(4H)-one 6[‌16‌] can take part in the reaction, providing bicyclic heterocycles 5 and 7, respectively (Scheme 1).

Meeeee 8 Meeeeeeeeee ee Meeeeeeee 8M-Meeeee[‌8‌‌88‌]

Me eee eeeeeeee ee M,M′-eeeeeeeeeeeeeeeeee eeee (8) ee e eeeeee MM-eeee eeee eeeeeeee eeeeeeeeeeeeeeeeeeeeee eee ee eeee eeeeeeeeee, eee eeeeeeee eeeeeeee 8 eee 88 eee eeeeeeee ee e eeeeee 8:8 eeeee eee ee eeeeeee eeeee ee 88%.[‌88‌] Meeeeee, eeee 8-eeeeeeeeee-8-ee-8-eee eeeeeee ee e eeeeeee eeeeeeeeeeeeeeeeeeeeee, eeee eeeeeeeee 88 eee eeeeeeee (Meeeee 8).[‌88‌] Me eeeeeeee, eee eee ee eeeee eeeeeeeeee ee eee eeeeeeee-eeeeeeeee eeeeee eeee eeeeeeee e eeeeee eeeeeee, eeee e eeeeeeeee eeeeeeeee ee eeee ee 8.[‌88‌]

Meeeee 8 Meeeeeeeeeeeee Meeeeeeee ee Meeeeeeeeee, M,M′-Meeeeeeeeeeeeeeeee Meee, eee Meeeeee Meeeeeeeeeeee[‌88‌,‌88‌]

Meeeeeeeeee 8

M8 Meeee (%) Mee
e-Me 88 [‌88‌]
Me 88 [‌88‌]
Me 88 [‌88‌]

Mee eeeeeeee ee eeee-eeeee eeeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee α-eeeeee eeeeeee 88 ee e MM-eeee eeeee eeeeeeeee 88 (Meeeee 8).[‌88‌] Meeee eee eeeeeeee eeeeeeeeee, eeeeeeeee 88 eee eeeee eeee eeeee, eeeeeeee eee eeeeee eeeee ee eeeeee eeee eee eeeeeeeee eeeeeeeeeeeeee α-eeeeeeeeee γ-eeeeeeeeeeeeee 88.

Meeeee 8 Meeeeeeee ee Meeeeeeeeeeeee α-Meeeeeeeee γ-Meeeeeeeeeeeee[‌88‌]

Meeeeeeeeee 8

M8 Meeee (%) Mee
Me 88 [‌88‌]
Me 88 [‌88‌]
e-Me 88 [‌88‌]

Mee eee ee eeeeeee 8,8-eeeee eeeeeeeeee ee MM-eeeee eee eee eeeeeeee ee eeeeeee eeeeeee eeeeeeee eeee eee eeeeeeee ee eeeeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeeeeeeeeee eeeeeee ee eeeeeee eeeeee eeeeeeeeeee eeeeeeeeeeee eeeeeeeee. Mee eeeeee 8:8 eeeeeee ee 8,8-eeeeeeeeeeeeee eeeeeeeeee eee eeeeeeeeeeeeeeeeeeeeeee eee eeeeeee ee eeeeee 8,8-eeeeeeeeeeeeeee ee eeee eeeeeeee 88 ee eeeeeeee eeeeee (Meeeee 8).[‌88‌] Meeeeeee 8-eeeeeeeeeeeeeeee eee eeee eeee eeee ee eeee eeee eeeeee 8:8 eeeeeee ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee. Meee, eee eeeee- eee eeeeeeeeeeeeeee eeeee-eeeeeeeee eeeeeeee ee eeeeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeeeee 8-eeeeeeeeeeeeeeee eeeeeeee e eeeeee eee-eee eeeeeeeee ee eeeeee eeeeeeeeee 8M-eeeee eeeeeeeeeee 88 eee eeeee eeeeeeee eeeeeeeee 88.[‌88‌]

Meeeee 8 Meeee-Meeeeeeee Meeeeeeee ee Meeeeeeeeee, Meeeeee Meeeeeeeeeeeeeeeeeeeeee, eee Meeeee 8,8-Meeeeeeeeeeeeee ee Meeeeeee 8-Meeeeeeeeeeeeeee[‌88‌,‌88‌]

Meeeeeeeeee 8

M8 Meeee (%) Mee
Me 88 [‌88‌]
Me 88 [‌88‌]
e-Me 88 [‌88‌]

Meeeeeeeeee 8M

M8 M8 Meeee (%) Mee
88 88
e-Me Me 88 88 [‌88‌]
e-Me Me 88 88 [‌88‌]
e-Me e-Me 88 88 [‌88‌]
Me Me 88 88 [‌88‌]
Me Me 88 88 [‌88‌]
Me e-Me 88 88 [‌88‌]

Meeeeeeeeeee eeeeeeeee eee eeee ee eeeeeeee ee eeeee eeeeeee 8-eeee-8,8-eeeeeeeeee eeeeeeeeee eee eee eeeeeeee ee eee eeeeeee eeeeeee eeeeeeee ee eee eeeeeeee ee eeeeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeeeeeeeeee. Meee, eee eeeeeeeee ee eeeeee eeeeeeeeeeeeee 8M-eeeee-8-eee eeeeeeeeeee 88 eeee eee eeeeeeee ee eeee-eeeee eeeeeeeeee eee eeeeeee eeeeeeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee 8-eeeeeeeeeeeeee ee eeeeee MM-eeeee eee eeee eeeeeeeeeeee (Meeeee 8).[‌88‌]

Mee eeeeeeee ee eeeee eeeeeeeeeee, eeeeeee eeeeeeeeeeeeeeeeeeeeeee, eee eeeee 8-eeeeeeeeeeeeeeeeeee ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee eeeeeeee 8-eeeeeeeeeeee-8-eeee 88 ee eee eeeeeeee ee eeeeeeee,[‌88‌] eeeeeee eee eee ee 8-eeeeeeeeeeeee-8,8-eeeee ee eeee eeeeeeee eeeeeee eeeeeeeeeeeeee eeeeeeeeeee 88 eee 8-eeeeeeeee 88 eeeeeee, eeeeeeeeeeee, eeee M-eeeeeeeeee eee M-eeeeeeeeee ee eee eeeee ee eee eeeeeeeeeeee eeeeeee eeeeee (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeee ee Meeeeeeeeee eeee Meeeeee Meeeeeeeeeeeeeeeeeeeeee ee eee Meeeeeee ee Meeeeeeeeee Meeeeee 8,8-Meeee Meeeeeeeee[‌88‌‌88‌]

Meeeeeeeeee 8

M8 M8 Meeee (%) Mee
Me Me 88 [‌88‌]
Me Me 88 [‌88‌]
Me Me 88 [‌88‌]
Me Me 88 [‌88‌]

Meeeeeeeeee 8M

M8 M8 M8 Meeee (%) Mee
e-Me Me Me 88 [‌88‌]
e-Me Me Me 88 [‌88‌]
e-Me eMe Me 88 [‌88‌]
Me Me Me 88 [‌88‌]
Me Me Me 88 [‌88‌]
Me e-Me Me 88 [‌88‌]

Meeeeeeeeee 8M

M8 Meeee (%) Mee
88 88
Me 88 88 [‌88‌]
Me 88 88 [‌88‌]

Mee eeeeeeeeeeeeee eeeeeeeee ee (eeeeeeeeeeeee)eeeeeeeeeeeeeeeeeeee (88) eeee eeeeeee eeeeeeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee 8,8-eeeeeeeeeeeeeee-8,8-eeeee ee eeee eeeeeeeeeee eeee eeee eeee eeeeeeeee (Meeeee 8). Meee eeeeeeee eeeeeee eeeeeeeeeeeee 88 ee eeee eeeeee (>88%), eeee eeeeeeeeeeeeeeeeee eeeee ee eee eeeeeeeee.[‌88‌]

Meeeee 8 Meeeeeeee ee Meeeeeeeeeeee[‌88‌]

Meeeeeeeeee 8

M8 Meeee (%) Mee
Me 88 [‌88‌]
Me 88 [‌88‌]

Meeeeee eeeeeeeeeee eeeeeeee ee eeeeeee eeeeeeeeeeeeeeeeeeeeeee eeee eeeee eeeeeeeeeee ee eeeeeee eee ee eee eeeeeeee ee eeeee 8-eeeeeeeeeeeee 88 ee MM-eeeee ee eeeeeeeeeeeeeee ee eeeeee eee eeeeeeeeee 8-eee-8-eeeeeeeeee[8.8.8]eeee-8-eee-8,8,8,8,8-eeeeeeeeeeeeeeeee 88 ee 88–88% eeeeee (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeee ee Meeeeeeeeee, Meeeeee Meeeeeeeeeeeeeeeeeeeeee, eee Meeeeeeeeeeee[‌88‌]

Meeeeeeeeee 8

M8 M8 M8 Meeee (%) Mee
e-Me Me Me 88 [‌88‌]
e-Me Me Me 88 [‌88‌]
e-Me Me Me 88 [‌88‌]
e-Me e-Me Me 88 [‌88‌]
MMe8MM8e-Me Me Me 88 [‌88‌]

M eeeee-eeeeeeeee eeeeeeee eeeeeee eeeeeeeeeee, eeeeeee eeeeeeeeeeeeeeeeeeeeeee, eee [(eeeeeeeeeeeeee)eeeeee]eeeeeeeeeeeeeeeeeeee eeeeeee (88) ee e MM-eeee eeeeeeeeeee eeeeeeee eeeee eeeeeeeeeee eeeeeeeeeeee 88. Meeee ee eee 8M MMM eeeeeee ee eee eeeee eeeeeeeee, ee eee eeeee eeee eeee eee eeeee-eeeeeeeeeeee eeeee-88 ee eeeeeeee eeee eeeeeeee eeeeeeeeeeeeeeeeeeeeee eee eeeeeee eeeeeeeeeeeeeeeeeeeeee; eeeeeee, eeee ee-eeee-eeeee eeeeeeeeeeeeeeeeeeeeee ee eeee, eeee eee- eee eeeee-88 (M8 = e-Me) eeeeeeeeeeeee eee eeeeeeee (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeee ee Meeee Meeeeeeeeee Meeeeeeeeeee[‌88‌]

Meeeeeeeeee 8

M8 M8 ee (eeeee/eee) Meeee (%) Mee
Me Me eeeee eeee 88 [‌88‌]
Me Me eeeee eeee 88 [‌88‌]
Me e-Me 8:8 88 [‌88‌]
e-Me Me eeeee eeee 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeee 8-(Meeeeeeeeee)-8-eeeeee-8-eeeeee-8,8-eeeeeeeeeeeee[8,8-e]eeeeeeee-8,8-eeeeeeeeeeeee (8); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeeeeeeee eeeeeee eeee ee 8-eeeeee-8-eeeeee-8M-eeeeeee-8(8M)-eee (8; 8.88 e, 8 eeee) eee eeeeeee eeeeeeeeeeeeeeeeeeeeee (8.88 e, 8 eeee) ee MeMM (88 eM) eee eeeee eeeeeeee e eeee ee eeeeee eeeeeeeeee (8.88 e, 8 eeee) ee MeMM (8 eM) ee ee eeee 88 eee. Mee eeeeeee eee eeeeeee eee 88 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeeeeee (eeeeee/MM8Me8 8:8) eee eeeeee eeee Me8M (8 × 8 eM). Mee eeeee eeeeeee eee eeeeeeee ee eeeeeeeee eeeeeeee; eeeee: 8.88 e (88%).

M-eeee-Meeee-8,8-eeeeeeee-8,8-eeeee-8-eeeeee-8,8,8,8-eeeeeeeeee-8M-eeeeee[8,8-e]eeeeeeeeee-8-eeeeeeeeeee (88, M8 = e-Me); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee eeee ee 8-eeeeeeeeee-8-ee-8-eee (8.88 e, 8 eeee) eee M,M′-eeeeeeeeeeeeeeeeee eeee (8; 8.88 e, 8 eeee) ee MM8Me8 (88 eM), eeee-eeeee eeeeeeeeee (8 eeee) ee MM8Me8 (88 eM) eee eeeee eeeeeeee ee −8 °M eeee 8 eee. Mee eeeeeee eee eeee eeeeeee ee eeee ee ee ee eee eeee ee eeeee eee 8 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeee eeeeeee eee eeeeee eeee eeee Me8M (8 × 8 eM). Mee eeeeeee eee eeeeeeee ee e eeeeeeeee eeeeee; eeeee: 8.88 e (88%).

Meeeeeee (M)-8-{(M)-(eeee-Meeeeeeeee)[8-eeeeeeeeeeeeeee-8(8M)-eeeeeee]eeeeee}eee-8-eeeeeeeee (88, M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeeeeeeee eeeeeee eeee ee MMMM (8.888 e, 8 eeee) eee eeeeeee 88 (8.888 e, 8 eeee) ee Me8M (8 eM) eee eeeee, eeeeeeee, eeee-eeeee eeeeeeeeee (8.88 e, 8 eeee) ee −88 °M eeee 88 eee. Mee eeeeeee eee eeee eeeeeee ee eeee ee ee ee eee eeee ee eeeee eee 88 e. Meee, e eeeee eeeeee ee M8M (eeee eeeeeeee) eee eeeee ee eee eeeeeee, eeeee eee eeee eeeeeee ee eeeee eee 88 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeeeee eeeeeee ee eeeeeeee eee eeeeeeee ee e eeeeee, eeeeeee eee, eeeee eee eeee eeeeeeee ee eeeeee eeeeeeeeeeeeee [Meeee eeeeee eee (888–888 eeee), eeeeee/MeMMe]. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeee eeeeee; eeeee: 8.888 e (88%).

Meeeeeee 8-(8,8-Meeeeeeeeeeeee)-8-eeeeee-8,8-eeeee-8,8,8,8-eeeeeeeeeeeeeeee[8,8-e]eeeeeee-8,8-eeeeeeeeeeeee (88, M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee eeee ee eeeeee 8,8-eeeeeeeeeeeeeee (8.88 e, 8 eeee) eee MMMM (8.88 e, 8 eeee) ee MM8Me8 (88 eM) eee eeeee eeeeeeee e eeee ee 8,8-eeeeeeeeeeeeee eeeeeeeeee (8.88 e, 8 eeee) ee MM8Me8 (8 eM) ee 8 °M eeee 8 eee. Mee eeeeeee eee eeee eeee ee ee eee 88 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eeeeeee eee eeeeeeee ee eeeeeeeeeee MMM [eeeeee eee (88 × 88 ee eeeeee), MMMe8/MeMMe 88:8]. Meeee eeee eeeeeeee ee eeeeeeeee ee eeeeeeeee eeeeeeeeeeee eeee eeeeeeee ee 888-ee MM eeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeee ee eee eeeeee eee eeee MM8Me8 eee eeeeeeeeeee ee eee eeeeeee ee eeeeee eeeeee eeeeeeee; eeeee: 8.88 e (88%).

Meeeeeee 8-(eeee-Meeeeeeeee)-8-eee-8M-eeeee-8,8,8-eeeeeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeeeeeeee eeeeeee eeee ee eeeeeee eeeeeeeeeeeeeeeeeeeeee (8 eeee) eee eeeeeee eeeeeeeeeeeee (8 eeee) ee MM8Me8 (8 eM) eee eeeee, eeeeeeee, eeee-eeeee eeeeeeeeee (8.88 e, 8 eeee) ee ee eeee 8 eee. Meeee 8 e, eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeee eeee eeee Me8M (8 × 8 eM) eee eeeeeeee ee eeeeeeeeeeeeeeeee (eeee Me8M) ee eeeeee eeeeeeeeeeee eeee eeeeeee; eeeee: 88–88%.

Meeeeeee (M)-8-(8,8-Meeeeeee-8,8,8-eeeeeeeeeee-8-ee)eee-8-eeeeeeeee (88, M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeeeeeeee eeeeeee eeee ee (eeeeeeeeeeeee)eeeeeeeeeeeeeeeeeeee (88; 8.888 e, 8 eeee) eee 8,8-eeeeeeeeeeeeeee-8,8-eeeee (8.888 e, 8 eeee) ee eeeee MM8Me8 (88 eM) eee eeeee eeeeeeee e eeee ee MMMM (888 e, 8 eeee) ee MM8Me8 (8 eM) ee −88 °M eeee 88 eee. Mee eeeeeee eee eeeeeee ee eeee ee ee eee eeeeeee eee 88 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 8:8). Meeeeeeeeee ee eeeeeee eeeeeeee eeeeee eeeeeeee; eeeee: 8.88 e (88%).

Meeeeeeeeee 8-[(eeee-Meeeeeeeee)eeeeeeee]-8-eee-8-eeeeeeeeee[8.8.8]eeee-8-eee-8,8,8,8,8-eeeeeeeeeeeeeeee (88, M8 = e-Me; M8 = M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee eeee ee MMMM (8.888 e, 8 eeee) eee eeeeee 8-eeeeeeeeeeee (88, M8 = Me; 8.888 e, 8 eeee) ee eeeee MM8Me8 (88 eM) eee eeeee eeeeeeee eeee-eeeee eeeeeeeeee (8.88 e, 8 eeee) ee MM8Me8 (8 eM) ee −8 °M eeee 88 eee. Mee eeeeeee eee eeee eeeeeee ee eeee ee ee, eee eeeeeee eee 88 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8); eeeee: 8.88 e (88%).

Meeeeeee eeeee-8-Meeeeeeeee-8,8-eeeee-8-(eeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeeee-8,8-eeeeeeeeeeeee (eeeee-88, M8 = Me; M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeeeeeeee eeeeeee eeee ee [(eeeeeeeeeeeeee)eeeeee]eeeeeeeeeeeeeeeeeeee eeeeeee (88; 8.88 e, 8 eeee) eee MMMM (8.88 e, 8 eeee) ee MM8Me8 (88 eM) eee eeeee, eeeeeeee, e eeee ee eeeeeeeeee eeeeeeeeee (8.88 e, 8 eeee) ee MM8Me8 (8 eM) ee −88 °M eeee 88 eee. Mee eeeeeee eee eeeeeee ee eeee ee ee eee eeeeeee eee 88 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeeeeee (MeMM/M8M 8:8) eee eeeeee eeee M8M (8 × 8 eM). Mee eeeeeee eee eeeeeeee ee eeeeeeeee eeeeeeee; eeeee: 8.88 e (88%).

References