Optical isomerism history

One-dimensional complexes, 6,134 One-dimensional conductors, 6,134 One-dimensional metals Krogmann salts, 6, 136 Optical isomerism cobalt ammines, 1,12 history, 1,180... 

The history of optical isomerism goes back to the year 1815, when the phenomenon was discovered by the French physicist Jean-Baptist Biot [1]. Optical activity was defined as the ability of a substance to rotate the plane of polarisation of light. Some years later, his student, Louis Pasteur [2] proposed that this optical activity of certain organic compounds was a consequence of their molecular asymmetry, that produces non-super-imposable mirror-image structures. A molecule which is not super-imposable on its mirror image is said to be chiral Conversely, a molecule which is superimposable on its mirror image is described as achiral... 

Several years ago, we developed a contrathermodynamic isomerization of a- to 3-pinene via diethylmyrtenylborane obtained from a-pinene by metalation-transmetalation.11 Later, (+)-p-pinene of > 99 % ee was prepared by this method.22 Extending this work to other bicyclic monoterpenes, the isomerization of (+)-2-, (+)-3-carene, and (-)-a-thujene, was studied.13 Among bicyclic monoterpene olefins with an exocyclic double bond, 3(10)-carene is a rare compound reported only a few times in the long history of terpene chemistry, and its rotation is still controversial.23,24 Sabinene is isolated from the oil of savin, and no convenient synthesis of an optically active sabinene is known. 

In September 1874 van t Hoff announced his theory of what he called the "asymmetric carbon atom" (a misleading phrase, since it is not the carbon atom itself but rather its chemical environment that van t Hoff conceived as asymmetric). Since this history has recently been well treated, I will provide only a brief account. First, van t Hoff drew attention to an empirical rule. He demonstrated that evidence known at that time was consistent with the thesis that whenever four different atoms or radicals are attached to any single carbon atom through its four valence units, a new kind of isomerism presents itself, one that is associated empirically with optical activity. He called any such carbon atom "asymmetric." In particular, there was no recognized case of an optically active organic compound that was known not to have an asymmetric carbon atom by this definition, somewhere in its structural formula. 

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