Hydrogenolysis of Nitrogen Heterocycles

To our knowledge, the only example of catalytic hydrogenolysis of a nitrogen heterocycle is the conversion of Py to a mixture of piperidine and various bis-(piperidinyl)alkanes catalyzed by Rh6(CO)i6 under water-gas shift conditions (150 °C, 800 psi CO) [35 d]. 

Over the last 15 years, the homogeneous studies of HDS and HDN processes have been extremely useful to understand many mechanistic details regarding the coordination of sulfur and nitrogen heterocycles to metal centers, hydrogen transfer from metal to coordinated heterocycle, metal insertion into C-S and C-N bonds, and the desulfurization/denitrogenation paths. Recently, however, there has been a qualitative leap in molecular catalysis so that crossing the border- 

DuPont s butadiene-to-adiponitrile synthesis (see Section 2.5.5.1 and [1]) and the Takasago synthesis of (-)-menthol from a-pinene (see Sections 2.9, 3.2.14.5, and 3.3.1). 

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