Neighboring group participation by carbonyl oxygen in nucleophilic substitution. Hydrolyses of [(9-Oxobenzonorbornen-2-yl)methyl]methyl(p-nitrophenyl)sulfonium tetrafluoroborate

1980 ◽  
Vol 45 (10) ◽  
pp. 1795-1800 ◽  
Author(s):  
Tadashi Irie ◽  
Hiroshi Tanida
Keyword(s):  
Nucleophilic Substitution ◽  
Carbonyl Oxygen ◽  
Neighboring Group ◽  
Group Participation ◽  
Methyl Methyl ◽  
Neighboring Group Participation

Participation of 19-ester groups in hypobromous acid additions to 2,3- and 5,6-unsaturated steroids

1979 ◽  
Vol 44 (5) ◽  
pp. 1483-1495 ◽  
Author(s):  
Pavel Kočovský ◽  
Václav Černý ◽  
Miroslava Synáčková
Keyword(s):  
Intramolecular Interaction ◽  
Ester Group ◽  
Carbonyl Oxygen ◽  
Cyclic Ether ◽  
Normal Reaction ◽  
Neighboring Group ◽  
Group Participation ◽  
Hypobromous Acid ◽  
Ether Oxygen ◽  
Neighboring Group Participation

Hypobromous acid action upon the 2,3-unsaturated acetoxy derivative Ia results in the formation of two products, the bromohydrin IVa and the cyclic ether VI as a product of the participation of ether oxygen of the ester group. Both these compounds are formed from the 2α,3α-bromonium ion XIIIa. Under the same conditions the 5,6-unsaturated 19-acetoxy derivative IIa afforded a mixture of the following products: Bromohydrin Xa as the product of a normal reaction course and the isomeric bromohydrin VIIa arising by intramolecular interaction with the carbonyl oxygen of the 19-acetoxy group. Both these compounds are formed from the 5α,6α-bromonium ion XVIIIa. The epimeric 5β,6β-bromonium ion XVIIa gives rise to the bromohydrin XIa. The mechanism of these reactions, difference in behavior of both olefins I and II and the competition between ambident neighboring group participation and external nucleophile attack is discussed.

Neighboring group participation in hypobromous acid addition to 19-substituted 5α-cholest-1-enes and in acid cleavage of their epoxy analogs

1982 ◽  
Vol 47 (11) ◽  
pp. 3062-3076 ◽  
Author(s):  
Václav Černý ◽  
Pavel Kočovský
Keyword(s):  
Neighboring Group ◽  
Group Participation ◽  
Acid Addition ◽  
Acid Cleavage ◽  
Hypobromous Acid ◽  
Neighboring Group Participation

Reactions of the title compounds (bearing an OH, OCH3 or OCOCH3 group at C(19)) involve 5(O)n, 7(O)π,n-participation by the 19-substituent or attack by an external nucleophile. The 6(O)π,n-participation does not occur. The behavior of 1,2-unsaturated (or epoxidated) compounds has been compared with the earlier described 2,3-unsaturated or epoxidated analogs. The 1,2-type is genarally less prone to participation. The reasons for this behavior are discussed.

Mechanism of acid cleavage of some steroid epoxides. Competition between neighboring group participation and external nucleophile attack

1982 ◽  
Vol 47 (1) ◽  
pp. 124-129 ◽  
Author(s):  
Pavel Kočovský ◽  
František Tureček ◽  
Václav Černý
Keyword(s):  
Perchloric Acid ◽  
Cyclic Ether ◽  
Oxirane Ring ◽  
Neighboring Group ◽  
Group Participation ◽  
Acid Cleavage ◽  
Neighboring Group Participation

The mechanism of perchloric acid cleavage of epoxides I and II was established on the basis of experiments using H2 18O. The 2α,3α-epoxide I gave two products: the cyclic ether V (60%) arising by 5(O)n participation of the 19-acetoxyl and the diol VI (40%). The latter compound is formed by two mechanisms: 1) By direct cleavage of the oxirane ring with H2 18O as external nucleophile and 2) by 7(O)π,n participation via the ion III. Under the same conditions the 5α,6α-epoxide II yielded two diols: The diequatorial diol VIII (96%) arising by 6(O)π,n participation and the diaxial diol IX which is again formed by both direct cleavage of the oxirane ring with H2 18O and by 7(O)π,n participation via the intermediate ion X. The competition of several mechanisms is discussed.

ChemInform Abstract: Remote Asymmetric Induction Using Neighboring Group Participation of a Sulfenyl Group.

ChemInform ◽  
2010 ◽  
Vol 25 (49) ◽  
pp. no-no
Author(s):  
Y. HASHIMOTO ◽  
Y. SATO ◽  
N. TAKESHITA ◽  
K. KUDO ◽  
K. SAIGO
Keyword(s):  
Asymmetric Induction ◽  
Neighboring Group ◽  
Group Participation ◽  
Neighboring Group Participation
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