Efficient convergent total syntheses of (+)-prosopinine (1) and (−)-deoxoprosophylline (4) were
accomplished using Rh−BIPHEPHOS complex-catalyzed cyclohydrocarbonylation as the key step.
The Rh−BIPHEPHOS complex-catalyzed cyclohydrocarbonylation of I, derived from (R)-serine, at
65 °C and 4 atm of CO and H2 (1:1) in ethanol afforded 6-ethoxypiperidine II, which was transformed
to enantiopure (+)-prosopinine (1) in 3 steps. In a similar manner, (−)-deoxoprosophylline was
synthesized through cyclohydrocarbonylation of IV derived from (S)-serine, giving 6-ethoxypiperidine
V. The key intermediate V was transformed to enantiopure (−)-deoxoprosophylline (4) in 4 steps.
These two short total syntheses clearly demonstrate the usefulness of the extremely regioselective
cyclohydrocarbonylation process developed in these laboratories for the concise syntheses of
piperidine alkaloids and related compounds.
Two types of silylcarbocyclization reactions (SiCaCs) of 1,6-diynes are discussed: (i) silylcarbocyclization−hydrosilylation (SiCaC−HS) reactions giving 3-(silylmethylene)-4-(silylmethyl)pyrrolidine, 3-(silylmethylene)-4-(silylmethyl)tetrahydrofuran, 3,4-bis(silylmethyl)-3-pyrroline, and 1,2-bis(silylmethyl)-4,4-dicarbethoxycyclopentene; and (ii) silylcarbobicyclization (SiCaB) reactions yielding a variety of carbocyclic
and heterocyclic bicyclo[3.3.0] systems. Mechanisms for these SiCaC−HS and SiCaB processes are proposed.
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