On the rearrangement of N-aryl-N-Boc-phosphoramidates to N-Boc-protected o-aminoarylphosphonates

作者：Kuliszewska Edyta; Hammerschmidt Friedrich^*

来源：Monatshefte fur Chemie, 2018, 149(1): 87-98.

DOI：10.1007/s00706-017-2058-x

• Phosphorus compounds
• Rearrangements
• Amines
• Carbanions
• Arenes

Various arylamines were converted in two steps to N-Boc-N-arylphosphoramidates. LiTMP and LDA induced directed ortho-metalation at temperatures from -78 to 0 A degrees C. The ensuing [1,3]-migration of the phosphorus atom with its substituents from the nitrogen to the ortho-carbanionic carbon atom gave N-Boc-protected o-aminoarylphosphonates. The nature of the substituent of 3-substituted phenylphosphoramidates strongly influenced the regioselectivity of phosphonate formation. A crossover experiment with a deuterated phosphoramidate proved the intramolecular course of the rearrangement. Three representative N-Boc-o-aminoarylphosphonates were deprotected to access the corresponding o-aminoarylphosphonic acids.
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• 出版日期2018-1