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Title: Pentacoordinate phosphoranes with reversed apicophilicity as stable intermediates in a Mitsunobu-type reaction
Authors: Satish Kumar, N.
Kommana, P.
Vittal, J.J. 
Kumara Swamy, K.C.
Issue Date: 20-Sep-2002
Citation: Satish Kumar, N., Kommana, P., Vittal, J.J., Kumara Swamy, K.C. (2002-09-20). Pentacoordinate phosphoranes with reversed apicophilicity as stable intermediates in a Mitsunobu-type reaction. Journal of Organic Chemistry 67 (19) : 6653-6658. ScholarBank@NUS Repository.
Abstract: Diisopropyl azodicarboxylate (DIAD) undergoes a cycloaddition reaction with the cyclic phosphites CH2(6-t-Bu-4-Me-C6H2O)2PX (1) [X = NCS (a), N3 (b), Cl (c), NHMe (d) and Ph (e)] to afford the novel pentacoordinate phosphoranes 2a-e as crystalline solids. This result is different from the reaction of PPh3 with DIAD used in the well-known Mitsunobu reaction. X-ray crystallography of 2a, 2b, and 2d reveals that the nitrogen, rather than the oxygen, occupies an apical position of the trigonal bipyramidal phosphorus. This is in violation of the commonly accepted preferences for substituents in trigonal bipyramidal phosphorus. In 2e, although the oxygen of the five-membered ring occupies the expected apical position, the phenyl group also occupies (the other) apical position, forcing the more electronegative oxygen atoms of the eight-membered ring to span equatorial-equatorial positions. In contrast to the above, the isocyanato compound CH2(6-t-Bu-4-Me-C6H2O)2-PNCO (1f), upon treatment with DIAD, affords compound 3 to which a tetracoordinate structure is assigned.
Source Title: Journal of Organic Chemistry
ISSN: 00223263
DOI: 10.1021/jo011150a
Appears in Collections:Staff Publications

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