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Stereospecific Pseudorotation of Diastereomeric Anti‐Apicophilic Spirophosphoranes: A Novel Stereochemical Transformation Involving 10‐P‐5 Phosphoranes
Author(s) -
Kojima Satoshi,
Nakamoto Masaaki,
Akiba Kinya
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200700968
Subject(s) - diastereomer , chemistry , phosphorane , stereospecificity , pseudorotation , stereochemistry , organic chemistry , ring (chemistry) , catalysis
A diastereomeric pair of monocyclic apical H‐phosphoranes ( 2‐ exo and 2‐ exo ) has been prepared from a diastereomeric pair of bicyclic equatorial H‐spirophosphoranes ( 1 ) with t BuLi. The thermal cyclization reaction of each diastereomeric apical H‐phosphorane gave rise to different diastereomeric O ‐equatorial anti‐apicophilic phosphoranes ( 3‐ exo and 3‐ endo , respectively) as single products. On the other hand, the oxidation reaction of each of these apical H‐phosphoranes was complementary to the thermal reaction, affording the opposite diastereomeric anti‐apicophilic phosphorane ( 3‐ endo and 3‐ exo , respectively) as a single product. The pseudorotation of each of these diastereomeric anti‐apicophilic phosphoranes ( 3‐ exo and 3‐ endo ) gave rise to different diastereomeric O ‐apical phosphoranes ( 4‐ exo and 4‐ endo , respectively) as single products.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)