- On the rearrangement of N-aryl-N-Boc-phosphoramidates to N-Boc-protected o-aminoarylphosphonates
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Abstract: 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?°C. The ensuing [1,3]-migration of the phosphorus atom with its substituents from the n
- Kuliszewska, Edyta,Hammerschmidt, Friedrich
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- PC-N-Heterocycles: Synthesis of biaryl-type 1,3-benzazaphospholes with ortho-substituted phenyl or 2-heteroaryl groups
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A facile synthesis of functionally substituted 2-(hetero)aryl 1,3-benzazaphospholes via nickel- or palladium-catalyzed phosphonylation of N-acyl-2-bromoanilides 1a-k with triethyl phosphite is presented. Anilidophosphonates 2a-g with naphthoyl-, o-substituted phenyl, furoyl- or thenoyl groups allow direct reductive cyclization with LiAlH4 to benzazaphospholes 3. The reaction of the o-bromoderivative 2d proceeds with concomitant replacement of bromine by hydrogen, whereas the electron-withdrawing pyridyl group of 2h prevents the synthesis of 3h by this short route. An alternative synthesis of 2-pyridylbenzazaphosphole 3hvia anilidophosphonates succeeded starting from Fmoc-anilinophosphonate 2kvia selective cleavage of the N-protecting group, reduction of the resulting phosphonoaniline to phosphinoaniline and cyclization with pyridine-2-carboxaldehyde via a dihydrobenzazaphosphole 8. N-Substituted pyridylmethylbenzazaphosphole 9 was detected as a side product. The structure elucidation of the new compounds is based on multinuclear NMR data and X-ray crystal structure analyses of a phosphonoanilide, underlining the dominance of N-H...OP hydrogen bonds over N-H...OC type hydrogen bonds, of 3h and a supramolecular associate of 3b and its unprecedented air oxidation product 10.
- Aluri, Bhaskar Reddy,Niaz, Basit,Kindermann, Markus K.,Jones, Peter G.,Heinicke, Joachim
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experimental part
p. 211 - 224
(2011/02/16)
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