Reagents and methods with low thermodynamic barriers can convert lower alkanes such as methane into methanol or other derivatives. One system uses a small quantity of a non-salt radical initiator such as Marshall's acid, a di-acid peroxide that can be split into two radicals. These radicals will remove hydrogens from methane, to generate methyl radicals. Sulfur trioxide is added, and methyl radicals combine with it to form methylsulfonate radicals. Methane is added, and the methylsulfonate radicals will remove hydrogens from it, to form stable methanesulfonic acid (MSA) while creating new methyl radicals to sustain the chain reaction. MSA that is removed can be sold or used, or it can be split into methanol (which can be used on site, or shipped as a liquid) and sulfur dioxide (which can be oxidized to sulfur trioxide and returned to the reactor). This anhydrous system creates no salts and minimal waste. An alternate system uses a bi-functional reagent with electrophilic and nucleophilic domains (such as a bromate-sulfate compound) to create coordinated proton and electron shifts in methane, using symphoric and anchimeric effects to create transitional intermediates with low energy barriers, allowing selective formation of intermediates that can be cracked to release methanol. Either system can improve the selectivity and yield of methanol from methane.