Journal
DALTON TRANSACTIONS
Volume 45, Issue 5, Pages 2008-2022Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5dt02860d
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Funding
- MICINN
- FEDER program [CTQ2011-27705, CTQ2014-5715P]
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The highly diastereoselective synthesis of P-stereogenic phosphinic amides via directed ortho lithiation (DoLi) of (S-C)-P,P-diphenylphosphinic amides with t-BuLi followed by electrophilic quench reactions is described. Functionalised derivatives containing a wide variety of ortho substituents (Cl, Br, I, OH, N-3, SiMe3, SnMe3, P(O)Ph-2, Me, allyl, (BuOCO)-Bu-t) have been prepared in high yields with diastereomeric ratios up to 98 : 2. The X-ray diffraction structure of the ortho-stannylated and ortho-iodo compounds showed that the pro-S P-phenyl ring was stereoselectively ortho-deprotonated by the organolithium base. The usefulness of the method is supported by two key transformations, the synthesis of P-stereogenic methyl phosphinates through replacement of the chiral auxiliary by a methoxy group and the first example of the insertion of benzyne into the P-N bond of a P-stereogenic phosphinic amide. A DFT study of this reaction showed that the insertion proceeds through a [2 + 2] cycloaddition and a subsequent ring-opening with retention of the P-configuration. Explorative coordination chemistry of the new P-stereogenic ligands provided access to a chiral phosphinic amide-phosphine oxide Zn(II) complex, the crystal structure of which is reported.
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