Synthetic Route of 6213-88-3,Some common heterocyclic compound, 6213-88-3, name is (E)-Methyl 3-iodoacrylate, molecular formula is C4H5IO2, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.
Method 1: To a dry Schlenk flask was added Pd(OAc)2 (36 mg,0.16 mmol), P(o-tol)3 (0.10 g, 0.33 mmol) and AgOAc (0.601 g,3.60 mmol). The flask was purged with argon, and dry, degassed MeCN (10 mL) was added. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.655 mL, 3.80 mmol) was then added, followed by methyl (2E)-3-iodoprop-2-enoate (0.704 g, 3.32 mmol). The vessel was purged further with argon, and the reaction mixture was then heated to 50 C with vigorous stirring for 2 days. The mixture was allowed to cool, then diluted with Et2O (280 mL) and passed through a short Celite/silica plug. The organic extracts were washed with 5% HCl (40 mL), H2O (80 mL) and brine (80 mL), dried over MgSO4, filtered and evaporated to yield 0.98 g of crude product as an orange oil. The crude product was purified by silica gel chromatography, eluent 10% EtOAc in hexane elution. Pure fractions were evaporated to yield (2E,4E)-5-(4,4,6-trimethyl-[1,3,2-dioxaborinan-2-yl]-penta-2,4-dienoic acid methyl ester as a yellow oil (0.404 g, 51%). 1H NMR (400 MHz, CDCl3): delta 1.35-1.24 (9H, m), 1.5-1.47 (1H, m), 1.81 (1H, dd, J = 14.0, 2.9 Hz), 3.75 (3H, s), 4.24 (1H, dqd, J = 12.3, 6.2, 2.9 Hz), 5.99-5.86 (2H, m), 6.97 (1H, ddd, J = 17.3, 11.0, 0.7 Hz), 7.33-7.21 (1H, m); 11B NMR (128 MHz, CDCl3): delta 25.52; 13C NMR (101 MHz, CDCl3): delta 23.58, 28.62, 31.65, 46.41,52.12, 65.52, 71.67, 123.17, 143.89, 146.54, 167.93; IR (upsilonmax, cm-1) 2974.3 (w) 1719.5 (s) inter alia; LCMS (ESI) 239.2; HRMS (ESI) calculated [C12H19BO4H] 238.1470, found 238.1491. Method 2: To a dry flask was added methyl (2E)-3-iodoprop-2-enoate (2.82 g, 13.3 mmol), Pd(OAc)2 (0.150 g, 0.67 mmol), P(otol)3 (0.408 g, 1.34 mmol) and AgOAc (2.41 g, 14.4 mmol). The flask was purged with argon, and dry, degassed MeCN (80 mL) wasadded. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (2.6 mL,15 mmol) was then added, the vessel was purged further with argon, and the reaction mixture was then heated to 50 C with vigorous stirring for 23h. The mixture was allowed to cool, then diluted with Et2O (200 mL) and passed through a short Celite/silicaplug. The organic extracts were washed with NH4Cl (200 mL), H2O(200 mL) and brine (200 mL), dried over MgSO4, filtered and evaporated to give crude product as a yellow oil (2.65 g, 83%). The compound was taken on to the next stage without any further purification or characterisation. Method 3: To a dry flask was added methyl (2E)- 3-iodoprop-2-enoate (2.82 g, 13.3 mmol), Pd(OAc)2 (0.15 g, 0.67 mmol), P(o-tol)3(0.408 g, 1.34 mmol) and AgOAc (2.41 g, 14.4 mmol). The flask was purged with argon, and dry, degassed MeCN (72 mL) was added. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (2.6 mL, 15 mmol) was then added, the vessel was purged further with argon, and the reaction mixture was then heated to 30 C with vigorous stirring for 19 h. The mixture was allowed to cool, then diluted with Et2O (200 mL) and passed through a short Celite/silica plug. The solvent was evaporated to give crude product as a yellow oil (2.84 g, 89%).The compound was taken on to the next stage without any further purification or characterisation. Method 4: To a dry flask was added methyl (2E)-3-iodoprop-2-enoate (1.0 g, 4.7 mmol), Pd(OAc)2 (0.011 g, 0.047 mmol), tri(2-furyl)phosphine (0.022 g, 0.094 mmol) and AgOAc (0.851 g, 5.11 mmol). The flask was purged with argon, and dry, degassed MeCN (28 mL) was added. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.93 mL, 5.4 mmol) was then added, the vessel was purged further with argon, and the reaction mixture was stirred vigorously at room temperature for 3 days. The mixture was diluted with Et2O (71 mL) and passed through a short Celite/silica plug. The solvent was evaporated to give crude product as a pale yellow oil (1.18 g, 99%). The compound was taken on to the next stage without any further purification or characterisation.
These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route (E)-Methyl 3-iodoacrylate, its application will become more common.
Reference:
Article; Madden, Katrina S.; Knowles, Jonathan P.; Whiting, Andrew; Tetrahedron; vol. 75; 45; (2019);,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com