Metalloporphyrin-catalyzed regioselective rearrangement of monoalkyl-substituted epoxides into aldehydes

Selective oxidation of terminal aryl and aliphatic alkenes to aldehydes catalyzed by iron(iii) porphyrins with triflate as a counter anion

“…The yield was determined by 1 H NMR with PhTMS as the internal standard. [3] CHO 2a 1 [3] [3] (14), 107 (13), 91(10). [4] [5] CHO Cl [6] (14), 125 (14), 88(10), 139(9).…”

“…[4] [5] CHO Cl [6] (14), 125 (14), 88(10), 139(9). [3] [7] [8] [8] [9] n-dodecanal [10] n-undecanal [11] n-palmitaldehyde [12] [13] [13] CHO 4e 1 [14] To a solution of [Fe(2,6-Cl 2 TPP)OTf] (4.4 mg, 0.004 mmol), styrene (62.4 mg, 0.6 mmol) and DCM (2 mL) was added PhIO (44.0 mg, 0.2 mmol). The resulting S7 heterogeneous mixture was stirred at room temperature for 6 h and then the solvent and excess styrene were removed under reduced pressure.…”

Three‐Membered Heterocycles. Structure and Reactivity

“…Generally, the regiochemistry is driven by two factors: (i) the stability of the nascent carbocation generated from ring opening and (ii) the migratory aptitude of the adjacent substituents. For example, the simple monoalkyl-substituted epoxide 564 (Scheme 2.83) undergoes regioselective rearrangement in the presence of iron(III)tetraphenylporphyrin to give the corresponding aldehyde (565) via a 1,2-hydride shift onto an incipient secondary cationic center [622], a process also promoted by sodium periodate under ambient conditions [623]. Terminal epoxides react with tetraallyltin in the presence of bismuth(III) triflate to give homoallylic alcohols 568.…”

A Novel Route to Organic–Inorganic Hybrid Nanomaterials

“…Suda's group has reported the use of chromium and iron porphyrins in organic synthesis. They used Cr(tpp)Cl for regioselective [3,3] rearrangement of aliphatic allyl vinyl ethers and for Claisen rearrangement of simple aliphatic allyl vinyl ethers, Fe(tpp)OTf for rearrangement of α,β‐epoxy ketones into 1,2‐diketones and rearrangement of monoalkyl‐substituted epoxides into aldehydes, and Cr(tpp)OTf for highly regio‐ and stereoselective rearrangement of epoxides to aldehydes 1–7…”