Reaction of Highly Volatile Organic Compounds with Organolithium Species in Flow Microreactor

Highly volatile organic compounds (VOCs) with boiling points (bp) around or below room temperature are generally difficult to manipulate precisely in liquid-phase organic reactions although they offer significant atom-economic advantages. We have developed a novel approach using a jacketed syringe pump to enable the formylation of organolithium species in a continuous-flow system under ambient pressure. Methyl formate (bp 32 degrees C) worked as a formylating agent and was successfully delivered to the continuous operation for over 30 minutes in our microflow system. This methodology was successfully expanded to the application of acetaldehyde (bp 21 degrees C) and heptafluoropropyl bromide (bp 12 degrees C).