論文発表
"Toward the Synthesis of Paspaline-Type Indole-Terpenes: Stereoselective Construction of Core Scaffold with Contiguous Asymmetric Quaternary Carbon Centers"
Ichiro Hayakawa*, Naochika Matsumaru, and Akira Sakakura*
J. Org. Chem. 2021, ASAP
DOI: 10.1021/acs.joc.1c01193
 

 
The core scaffold of paspaline-type indole-terpenes was synthesized by using the House–Meinwald rearrangement as a key step. Rearrangement of the epoxide methyl group in the precursor with methylaluminum bis(4-bromo-2,6-di- tert-butylphenoxide) as a Lewis acid proceeded smoothly to construct contiguous asymmetric quaternary carbon centers by a 1,2-chirality transfer.
(2021.7.7)

論文発表
"Strain-Release Difunctionalization of C–C σ- and π-bonds of an Organoboron Ate-Complex through 1,2-Metallate Rearrangement"
Haruki Mizoguchi,* Akira Sakakura*
Chem. Lett.  2021, 50, 792–799.
DOI: 10.1246/cl.200926
 

 
This highlight review describes the recent development of an electrophile-triggered 1,2-metallate rearrangement of organoboronic ester ate-complex, which proceeds through 1,2-difunctionalization of carbon–carbon σ- and π-bonds, using strain energy as a driving force. Coupling reactions of small ring carbocyclic boronic esters, such as cyclopropyl-, bicyclo[1.1.0]butyl-, and cyclopropenyl-boronic ester, are summarized along with the proposed reaction mechanisms and representative examples.