Highly Selective 1,4‐ and 1,6‐Addition of P(O)?H Compounds to p‐Quinones: A Divergent Method for the Synthesis of C‐ and O‐Phosphoryl Hydroquinone Derivatives |
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| Authors: | Biquan Xiong Ruwei Shen Midori Goto Shuang‐Feng Yin Li‐Biao Han |
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| Institution: | 1. Department of Chemistry, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082 (P. R. China), Fax: (+86)?731‐88821310;2. National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305‐8565 (Japan);3. State Key Laboratory of Materials‐Oriented, Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009 (P. R. China) |
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| Abstract: | The reaction of P(O)? H compounds with p‐quinones could proceed through either 1,4‐ or 1,6‐addition pathways by employing different additives to selectively give the corresponding C‐ and O‐phosphoryl hydroquinone derivatives in good yields. Oxidative double 1,4‐addition of P(O)? H compounds to p‐quinones was also achieved by tuning the solvent, affording a facile synthesis of bis‐substituted hydroquinones with phosphorus functionality. Further studies on these reactions by using optically active H‐phosphinates showed that all addition reactions took place stereospecifically with retention of configuration at the phosphorus center. The findings lead to the establishment of a divergent method for the synthesis of C‐ and O‐phosphoryl hydroquinone derivatives from easily available P(O)? H compounds. |
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| Keywords: | nucleophilic addition enantioselectivity phosphorus quinones |
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