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Di(hydroperoxy)alkane Adducts of Phosphine Oxides: Safe, Solid, Stoichiometric, and Soluble Oxidizing Agents
Author(s) -
Ahn Shin Hye,
Bhuvanesh Nattamai,
Blümel Janet
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703676
Subject(s) - adduct , oxidizing agent , phosphine , alkane , chemistry , stoichiometry , medicinal chemistry , organic chemistry , hydrocarbon , catalysis
The di(hydroperoxy)alkane adducts of phosphine oxides 1 – 9 , Ph 3 PO⋅(HOO) 2 CMe 2 , Cy 3 PO⋅(HOO) 2 CMe 2 , Ph 3 PO⋅ (HOO) 2 CMeEt, Cy 3 PO⋅(HOO) 2 CMeEt, Cy 3 PO⋅(HOO) 2 CEt 2 , Cy 3 PO⋅ (HOO) 2 C(CH 2 ) 5 , Cy 3 PO⋅(HOO) 2 CMePh, (Ph 2 P(O)CH 2 CH 2 P(O)Ph 2 )⋅ ((HOO) 2 CEt 2 ) 2 , and Ph 2 P(O)CH 2 P(O)Ph 2 ⋅(HOO) 2 CMe 2 , respectively, are synthesized and fully characterized by 1 H, 13 C, and 31 P NMR, and IR spectroscopies. Single crystal X‐ray structures are reported for 3 – 9 . Different one‐pot synthetic pathways, starting from R 3 P, R 3 PO, R 3 PO⋅H 2 O, and R 3 PO⋅H 2 O 2 are explored and discussed and a mechanism for the formation of the di(hydroperoxy)alkane adducts of phosphine oxides is suggested. The longevity of the adducts is tested by monitoring the oxidation of Ph 3 P with quantitative NMR. The solubilities of the adducts in organic solvents are presented, and their applicability as stoichiometric oxidizing agents for the selective oxidation of sulfides to sulfoxides is reported.