Cyclopropanes in water: a diastereoselective synthesis of substituted 2H-chromen-2-one and quinolin-2(1H)-one linked cyclopropanes

Abstract

A one-pot three component reaction has been developed for the synthesis of substituted cyclopropanes employing 4-bromomethyl-2H-chromen-2-one/quinolin-2(1H)-ones, aromatic aldehydes and activated nitriles.

In Situ Generation of Quinolinium Ylides from Diazo Compounds: Copper-Catalyzed Synthesis of Indolizine

“…■ EXPERIMENTAL DATA OF PRODUCTS 7, 162.9, 160.3, 137.3, 132.3, 130.4, 128.3, 128.1, 128.0, 125.3, 124.9, 119.2, 117.4, 117.1, 104.7, 61.3, 52.3, 51.3, 13.6 (d,J = 8.8 Hz,1H), 4.43 (q, J = 7.1 Hz, 2H), 3.99 (s, 3H), 3.90 (s, 3H), 2.47 (s, 3H), 1.40 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 165. 7, 162.9, 160.3, 137.1, 135.2, 130.4, 130.2, 129.4, 127.9, 127.8, 124.9, 118.9, 117.2, 117.0, 104.5, 61.2, 52.2, 51.2, 20.4, 13.6; HRMS (ESI-TOF) m/ z [M + H] + calcd for C 20 H 20 NO 6 370.1285, found 370.1277; IR (neat, cm −1 ) υ 3037, 1690, 1447, 1219, 1183, 1083, 816. 1-Ethyl 2,3-Dimethyl 7-Methoxypyrrolo[1,2-a]quinoline-1,2,3-tricarboxylate (4c): yellow solid; yield 188 mg (98%); mp 124.7−126.4 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.15 (d, J = 9.4 Hz, 1H), 8.04 (d, J = 9.4 Hz, 1H), 7.49 (d, J = 9.4 Hz, 1H), 7.17 (dd, J = 9.4, 2.9 Hz, 1H), 7.11 (d, J = 2.8 Hz, 1H), 4.42 (q, J = 7.1 Hz, 2H), 3.98 (s, 3H), 3.89 (s, 6H), 1.40 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 165.…”

“…8, 162.9, 160.3, 156.6, 136.6, 130.2, 127.8, 126.9, 126.2, 120.7, 117.4, 117.1, 117.0, 108.9, 104.5, 61.2, 55.1, 52.2, 51.2, 13.6 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 165. 4, 162.6, 160.1, 137.0, 130.9, 130.7, 130.7, 128.1, 127.2, 126.8, 126.1, 120.8, 118.4, 117.6, 105.2, 61.4, 52.3, 51.4, 13.5 (d,J = 9.4 Hz,1H), 4.42 (q, J = 7.1 Hz, 2H), 3.99 (s, 3H), 3.91 (s, 3H), 1.40 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 165. 4, 162.6, 160.1, 137.0, 131.1, 130.9, 130.7, 130.3, 126.7, 126.4, 121.0, 118.7, 118.3, 117.6, 105.3, 76.9, 76.6, 76.2, 61.4, 52.3, 51.4, 13.5 8, 163.0, 160.3, 137.5, 135.5, 132.1, 130.6, 127.8, 125.2, 125.1, 124.6, 119.6, 116.9, 116.6, 103.6, 61.2, 52.2, 51.2, 19.0, 13.6; HRMS (ESI-TOF) m/ z [M + H] + calcd for C 20 H 20 NO 6 370.1285, found 370.1291; IR (neat, cm −1 ) υ 2957, 1699, 1444, 1260, 1165, 1013, 758. 1-Ethyl 2,3-Dimethyl 9-Methylpyrrolo[1,2-a]quinoline-1,2,3tricarboxylate (4g): light yellow solid; yield 33 mg (18%); mp 147.1−150.1 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.14 (d, J = 9.2 Hz, 1H), 7.61 (dd, J = 7.1, 1.8 Hz, 1H), 7.57 (d, J = 9.3 Hz, 1H), 7.48− 7.37 (m, 2H), 4.32 (q, J = 7.1 Hz, 2H), 4.00 (s, 3H), 3.91 (s, 3H), 2.51 (s, 3H), 1.31 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 165.…”

“…5, 161.2, 139.4, 132.8, 128.2, 128.1, 128.1, 125.8, 125.1, 124.7, 122.9 (q, J = 122.8 Hz), 120. 5, 119.6, 116.8, 104.6, 59.5 (q, J = 110.1 Hz), 59.0, 13.9; 19 (d,J = 8.7 Hz,1H),8.20 (d,J = 9.3 Hz,1H),7.93 (s,1H),7.71 (d,J = 7.8 Hz,1H),1H),7.51 (d,J = 9.3 Hz,1H),7.44 (t,J = 7.5 Hz,1H),4.47 (m,J = 5.4,3.7 Hz,2H), 4.43 (q, J = 7.1 Hz, 2H), 4.03−3.93 (m, 2H), 2.61 (s, 1H), 1.44 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 163. 9, 161.2, 139.0, 132.8, 128.1, 127.8, 127.5, 125.8, 124.9, 124.6, 120.0, 119.5, 117.0, 106.1, 65.5, 61.1, 60.7, 13.9; HRMS (ESI-TOF) m/z [M + H] + calcd for C 18 H 18 NO 5 328.1179NO 5 328. , found 328.1175; IR (neat, cm −1 ) υ 2982, 1701, 1545, 1178, 1083, 1029, 756. 3-Cyclohexyl 1-Ethyl Pyrrolo[1,2-a]quinoline-1,3-dicarboxylate (4n): light yellow solid; yield 75 mg (41%); mp 66.6−68.8 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.36 (d,J = 8.7 Hz,1H),8.25 (d,J = 9.3 Hz,1H),7.95 (s,1H),7.70 (dd,J = 7.9,1.4 Hz,1H),7.55 (ddd,J = 8.7,7.2,1.5 Hz,1H),7.51 (d,J = 9.3 Hz,…”

Water Soluble Coumarin Quaternary Ammonium Chlorides: Synthesis and Biological Evaluation

“…[12][13][14][15][16][17] Anand et al used CQACs as intermediate for the synthesis of coumarincyclopropanes in water. [18] According to our knowledge, only Melikyan et al synthesized cyano or benzothiazolyl substituted coumarin pyridinium or quinolinium iodides and tested their antimicrobial properties. [19] Therefore, in this study, we aimed to synthesis and biological evaluation of CQACs due to three main reasons: (i) the limited numbers of studies in this area, (ii) biological importance of both coumarin derivatives and QACs, and (iii) increasing water solubility.…”

Diastereoselective Cyclopropanation through Michael Addition‐Initiated Ring Closure between α,α‐Dibromoketones and α,β‐Unsaturated Fischer Carbene Complexes

“…The MIRC reaction can also deliver a tetrasubstituted cyclopropane skeleton through the organocatalytic addition of aldehydes and bromomalonates to the Michael acceptors. Moreover, α‐oxo esters, nitromethane, phosphonate and pyridinium salts have been used as nucleophiles. Some examples of the MIRC cyclopropanation reaction between α,β‐unsaturated alkoxy carbenes, and 2‐methoxyfuran, sulfur ylides, lithiated epoxides, and lithiated dihalomethanes were used to prepare di‐, tri‐, and tetrasubstituted cyclopropanes.…”