Cyclodiphosphazanes as synthetic probes: P-C/P-N bond formation from the reaction with functionalized propargyl alcohols and 𝑁-hydroxy substrates

Journal of Chemical Sciences

K C Kumara Swamy1¹  G Gangadhararao¹ 

[1] School of Chemistry, University of Hyderabad, Hyderabad 500 046, India$$

关键词: Cyclodiphosphazanes;    cis–trans isomerism;    allenes;    indoles;    rearrangement;    propargyl alcohols;    phosphano-heterocycles.;   

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

Phosphano-indoles were synthesized in a fairly straightforward route from the reaction of simple cyclodiphosphazanes [XP(𝜇-N-t-Bu)2PY] [X=Y=NH-𝑡-Bu (1a); X=Y=NH-i-Pr (1b)] with o-aminophenyl functionalized propargyl alcohols. The reaction occurs via an allene intermediate formed by PIII-O-C→PV(O)-C rearrangement, followed by cyclization utilizing the central allenic carbon and the –NH2 functionality. In a similar way, cyclodiphosphazanes [XP(𝜇-N-t-Bu)2PY] [X=Y=Cl (1c); X=Cl, Y=NH-𝑡-Bu(1d)] have been treated with N-hydroxy substrates to obtain novel PIII-O-N→PV(O)-N rearranged products.X-ray structures of the four products, 2-(1-phenyl-ethyl)-3-[(t-Bu)NH)P(𝜇-N-𝑡-Bu)2P(O)]-indole [14], cis-{[-C(=O)-C6H4-C(=O)-]-N-P(=O)-N-t-Bu}2[cis-18], trans-{[-C(=O)-C6H4-C(=O)-]-N-P(=O)-N-𝑡-Bu}2 [trans-18] and cis-[(𝑡-BuNH)P(𝜇-N-t−Bu)2P(=O)-N{-C(=O)-CH2-CH2-C(=O)-}] [cis-19] are also reported

【 授权许可】

Unknown