1980
DOI: 10.1021/jo01300a017
|View full text |Cite
|
Sign up to set email alerts
|

Thermolyses of 3-alkyl-4-phenyl-2-oxetanones and related compounds

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1

Citation Types

2
9
0

Year Published

1980
1980
2012
2012

Publication Types

Select...
10

Relationship

0
10

Authors

Journals

citations
Cited by 23 publications
(11 citation statements)
references
References 1 publication
2
9
0
Order By: Relevance
“…In view of the fact that thiolates are well-known to open β-lactones by S N 2 attack at the β-position, this remarkable reaction might be viewed as an intramolecular S N 2-like process involving a bicyclo[2.2.0]hexane-like transition state made possible by the relatively long C-S bonds, both existing and incipient (Scheme 3, path a). Alternatively, taking note of the widely accepted stepwise zwitterionic intermediate model for the extrusion of CO 2 from β-lactones, [38][39][40][41][42][43][44][45][46][47][48] it may be considered as arising from trapping of a transient zwitterionic form of the lactone (Scheme 3, path b). While the elucidation of the mechanism of formation of 13 from 4 must await further work, the formation of 13 serves to underline the preference of β-lactones toward nucleophilic ring opening at the β-position by soft nucleophiles [49][50][51][52][53][54][55][56] even though the nucleophile is ideally placed for attack on the carbonyl centre.…”
Section: Resultsmentioning
confidence: 99%
“…In view of the fact that thiolates are well-known to open β-lactones by S N 2 attack at the β-position, this remarkable reaction might be viewed as an intramolecular S N 2-like process involving a bicyclo[2.2.0]hexane-like transition state made possible by the relatively long C-S bonds, both existing and incipient (Scheme 3, path a). Alternatively, taking note of the widely accepted stepwise zwitterionic intermediate model for the extrusion of CO 2 from β-lactones, [38][39][40][41][42][43][44][45][46][47][48] it may be considered as arising from trapping of a transient zwitterionic form of the lactone (Scheme 3, path b). While the elucidation of the mechanism of formation of 13 from 4 must await further work, the formation of 13 serves to underline the preference of β-lactones toward nucleophilic ring opening at the β-position by soft nucleophiles [49][50][51][52][53][54][55][56] even though the nucleophile is ideally placed for attack on the carbonyl centre.…”
Section: Resultsmentioning
confidence: 99%
“…Apart from the computational studies, several authors have proposed different mechanistic models to explain their experimental results. Thus, nonplanar supra − antara (Scheme 1, mechanism b) transition structures have been proposed by Nishida et al , in agreement with the classical Woodward−Hoffmann mechanism. However, many experimentalists have proposed a two-step mechanism, (Scheme 1, mechanism c) in which the O1−C4 bond is broken via transition structure TS1 to form an intermediate INT .…”
Section: Introductionsupporting
confidence: 67%
“…The pericyclic extrusion of CO 2 from β-lactones is a well-known reaction . However, the rate constants (10 -1 −10 -4 s -1 ) for this type of cleavage are typically several orders of magnitude slower than even the cyclobutylcarbinyl rearrangement and therefore such chemistry was not expected to be a serious complication in this study. Here, we report in full our study of the free radical chemistry of 4-oxetanonylcarbinyl radicals …”
Section: Introductionmentioning
confidence: 86%