Stereochemistry of substitution at trico-ordinate phosphorus
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Stereochemistry of substitution at trico-ordinate phosphorus. / Nielsen, John; Dahl, Otto.
I: Journal of the Chemical Society, Perkin Transactions 2, Nr. 3, 01.12.1984, s. 553-558.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Stereochemistry of substitution at trico-ordinate phosphorus
AU - Nielsen, John
AU - Dahl, Otto
PY - 1984/12/1
Y1 - 1984/12/1
N2 - A series of reactions of ring-substituted 1,3,2-dioxaphospholanes, 1,3,2-oxazaphospholanes, 1,2-oxaphospholes, and phosphetanes bearing the leaving groups Cl, OR, or NR2 on phosphorus, with the nucleophiles HCl, MeO-, MeOH, PhOH, Me2NH, Et2NH, and [CH 2]5NH have been studied. N.m.r. signals (1H and 31P) from reactant and product diastereoisomers have been assigned, and the stereo-chemistry of the substitution reactions have been determined by 31P n.m.r. monitoring. The outcome varies from complete inversion to complete lack of stereoselectivity. During the initial stages many of the non-selective reactions proceed with predominant inversion, and most of the results may be interpreted by assuming that the actual substitution step occurs with inversion, and that the lack of stereoselectivity is due to competing isomerizations of products or reactants. Exceptions are certain reactions where the leaving group is Cl; these appear to involve a non-selective substitution step.
AB - A series of reactions of ring-substituted 1,3,2-dioxaphospholanes, 1,3,2-oxazaphospholanes, 1,2-oxaphospholes, and phosphetanes bearing the leaving groups Cl, OR, or NR2 on phosphorus, with the nucleophiles HCl, MeO-, MeOH, PhOH, Me2NH, Et2NH, and [CH 2]5NH have been studied. N.m.r. signals (1H and 31P) from reactant and product diastereoisomers have been assigned, and the stereo-chemistry of the substitution reactions have been determined by 31P n.m.r. monitoring. The outcome varies from complete inversion to complete lack of stereoselectivity. During the initial stages many of the non-selective reactions proceed with predominant inversion, and most of the results may be interpreted by assuming that the actual substitution step occurs with inversion, and that the lack of stereoselectivity is due to competing isomerizations of products or reactants. Exceptions are certain reactions where the leaving group is Cl; these appear to involve a non-selective substitution step.
M3 - Journal article
AN - SCOPUS:37049099281
SP - 553
EP - 558
JO - Royal Chemical Society. Journal. Perkin Transactions 2
JF - Royal Chemical Society. Journal. Perkin Transactions 2
SN - 1472-779X
IS - 3
ER -
ID: 131117193