The manipulation of the stereochemical outcome of a specific reaction is commonly achieved through the use of transition metal catalysts bearing a chiral ligand or through the use of a resolved organocatalyst. This requirement adds considerable challenges to the synthesis, and in some cases, the selective preparation of a target substrate with the desired
68%
> 10 related examples up to 85%
OMe
OMe
OMe
OMe 1) PIFA (1.2 equiv)
HFIP, rt 2) TMSN3 (5 equiv)
rt, 15 min N3
SCHEmE 1.20 Metal‐free C–H azidation of electron‐rich arenes [93].
96%
>15 related examples up to 99%
Me
O NH2
NH3 (2 equiv, aq) NIS (20%) TBHP (4 equiv)
DMA, 120 °C
Me
N N
SCHEmE 1.21 C–H oxidative amination reaction [94].
REFERENCES 33 stereochemistry is not possible. Both transition metal and organocatalyzed approaches have their merits, and the most successful system will depend upon the reaction as well as the nature of the substrates. One of the consistent issues with asymmetric synthesis remains the substrate specificity inherent to many catalysts. It is quite common for the enantioselec-tivity of a new reaction to be extremely high for only three to four substrates. Furthermore, reports that list the selectivity for only one to two substrates are of limited value unless those specific substrates are known to be troublesome.
To this end, the burden is on the synthetic community to continue to develop active catalysts with greater selectivity and increased substrate scope. The following chapters will highlight asymmetric reactions for the formation of functional groups through the formation of carbon–heteroelement bonds with special attention paid to reactions that are highly selective but also to those that show the largest substrate scope.
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