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Title: Diverse Modes of Reactivity of 6-(Chloromethyl)-6-methylfulvene: Diverse Modes of Reactivity of 6-(Chloromethyl)-6-methylfulvene
PAR ID:
10035601
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
European Journal of Organic Chemistry
Volume:
2017
Issue:
20
ISSN:
1434-193X
Page Range / eLocation ID:
2925 to 2931
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract

    The reaction of an aryne with an alkyne to generate a benzocyclobutadiene (BCB) intermediate is rare. We report here examples of this reaction, revealed by Diels–Alder trapping of the BCB by either pendant or external electron‐deficient alkynes. Mechanistic delineation of the reaction course is supported by DFT calculations. A three‐component process joining the benzyne first with an electron‐rich and then with an electron‐poor alkyne was uncovered. Reactions in which the BCB functions in a rarely observed role as a 4π diene component in Diels–Alder reactions are reported. The results also shed new light on aspects of the hexadehydro‐Diels–Alder reaction used to generate the benzynes.

     
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    The reaction of an aryne with an alkyne to generate a benzocyclobutadiene (BCB) intermediate is rare. We report here examples of this reaction, revealed by Diels–Alder trapping of the BCB by either pendant or external electron‐deficient alkynes. Mechanistic delineation of the reaction course is supported by DFT calculations. A three‐component process joining the benzyne first with an electron‐rich and then with an electron‐poor alkyne was uncovered. Reactions in which the BCB functions in a rarely observed role as a 4π diene component in Diels–Alder reactions are reported. The results also shed new light on aspects of the hexadehydro‐Diels–Alder reaction used to generate the benzynes.

     
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