Abstract
We have experimentally proved the unsymmetrical 1,1-diboration of diazo compounds, formed in situ from aldehydes and cyclic and non-cyclic ketones, in the absence of any transition metal complex. The heterolytic cleavage of the mixed diboron reagent, Bpin-Bdan, and the formation of two geminal C-Bpin and C-Bdan bonds has been rationalised based on DFT calculations to occur via a concerted-asynchronous mechanism. Diastereoselection is attained on substituted cyclohexanones and DFT studies provide understanding on the origin of the selectivity. The alkoxide-assisted selective deborylation of Bpin from multisubstituted sp3-carbon and generation of a Bdan stabilized carbanion, easily conducts a selective protodeboronation sequence.
Original language | English |
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Pages (from-to) | 9659-9664 |
Number of pages | 6 |
Journal | Organic and Biomolecular Chemistry |
Volume | 13 |
Issue number | 37 |
DOIs | |
Publication status | Published - 29 Jul 2015 |
Externally published | Yes |
Keywords
- Gem-dimetallic compounds
- Tertiary boronic esters
- Asymmetric-synthesis
- Hydroboration
- Diborylation
- Insertion
- Diborylmethane
- Construction
- Derivatives
- Cyclopropyl