text: As a doctoral student at the University of Chicago, Herbert Brown studied the reactions of diborane, BH. Hermann Irving Schlesinger's laboratory at the University of Chicago was one of two laboratories that prepared diborane. It was a rare compound that was only prepared in small quantities. Schlesinger was researching the reactions of diborane to understand why the simplest hydrogen-boron compound is BH instead of BH.
   When Brown started his own research, he observed the reactions of diborane with aldehydes, ketones, esters, and acid chlorides. He discovered that diborane reacts with aldehydes and ketones to produce dialkoxyboranes, which are hydrolyzed by water to produce alcohols. Until this point, organic chemists did not have an acceptable method of reducing carbonyls under mild conditions. Yet Brown's Ph.D. thesis published in 1939 received little interest. Diborane was too rare to be useful as a synthetic reagent.
  In 1939, Brown became the research assistant in Schlesinger's laboratory. In 1940, they began to research volatile, low molecular weight uranium compounds for the National Defense Research Committee. Brown and Schlesinger successfully synthesized volatile uranium(IV) borohydride, which had a molecular weight of 298. The laboratory was asked to provide a large amount of the product for testing, but diborane was in short supply. They discovered that it could be formed by reacting lithium hydride with boron trifluoride in ethyl ether, allowing them to produce the chemical in larger quantities. This success was met with several new problems. Lithium hydride was also in short supply, so Brown and Schlesinger needed to find a procedure that would allow them to use sodium hydride instead. They discovered that sodium hydride and methyl borate reacted to produce sodium trimethoxyborohydride, which was viable as a substitute for the lithium hydride.
  Soon they were informed that there was no longer a need for uranium borohydride, but it appeared that sodium borohydride could be useful in generating hydrogen. They began to look for a cheaper synthesis and discovered that adding methyl borate to sodium hydride at 250° produced sodium borohydride and sodium methoxide. When acetone was used in an attempt to separate the two products, it was discovered that sodium borohydride reduced the acetone.
  Sodium borohydride is a mild reducing agent that works well in reducing aldehydes, ketones, and acid chlorides. Lithium aluminum hydride is a much more powerful reducing agent that can reduce almost any functional group. When Brown moved to Purdue University in 1947, he worked to find stronger borohydrides and milder aluminum hydrides that would provide a spectrum of reducing agents. The team of researchers at Purdue discovered that changing the metal ion of the borohydride to lithium, magnesium, or aluminum increases the reducing ability. They also found that introducing alkoxy substituents to the aluminum hydride decreases the reducing ability. They successfully developed a full spectrum of reducing agents.
   While researching these reducing agents, Browns coworker, Dr. B. C. Subba Rao, discovered an unusual reaction between sodium borohydride and ethyl oleate. The borohydride added hydrogen and boron to the carbon-carbon double bond in the ethyl oleate. The organoborane product could then be oxidized to form an alcohol. This two-step reaction is now called hydroboration-oxidation and is a reaction that converts alkenes into anti-Markovnikov alcohols. Markovnikovs rule states that, in adding hydrogen and a halide or hydroxyl group to a carbon-carbon double bond, the hydrogen is added to the less-substituted carbon of the bond and the hydroxyl or halide group is added to the more-substituted carbon of the bond. In hydroboration-oxidation, the opposite addition occurs.