Beilstein J. Org. Chem.2019,15, 285–290, doi:10.3762/bjoc.15.25
Abstract The synthesis of 1,2-divinylcyclopropanes by the reaction of cyclopropenes with 1,3-dienes is reported. The process relies on the ability of ZnCl2 or [Rh2(OAc)4] to generate metal–vinyl carbene intermediates from cyclopropenes, which effect cyclopropanation of 1,3-dienes. Most of the reactions
proceeded in reasonable yields while the diastereoselectivity strongly depends on the structure of the diene. An example of an intramolecular process as well as the use of furan and 1,4-cyclohexadiene as dienes are also reported.
Keywords: cyclopropanation; cyclopropenes; dienes; divinylcyclopropanes
allows sigmatropic rearrangements leading to odd-numbered carbocyclic derivatives [8]. In this sense, seven-membered carbocycles, namely 1,4-cycloheptadienes, can be forthrightly prepared from cis- or trans-1,2-divinylcyclopropanes through a Cope rearrangement [8][9]. The potential of this type of
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Graphical Abstract
Scheme 1:
Typical syntheses of 1,2-divinylcyclopropanes and rationale hypothesis for their syntheses from cyc...
Beilstein J. Org. Chem.2014,10, 163–193, doi:10.3762/bjoc.10.14
(see Scheme 9) [48] was added to ketone 45 followed by elimination to give a mixture of trans/cis-divinylcyclopropanes 47/48. Photoepimerization at the temperature required for cis-DVCPR (98 °C, trans-DVCPR occurred above 140 °C) gave bicyclic 49 in good yields. (±)-Confertin (50) and (±)-damsinic acid
give intermediate vinyl-allenecyclopropane 249, followed by a DVCPR to furnish cycloheptadiene 250.
1,2-Shift and vinyl-carbenoid formation sequences
Two major pathways to generate divinylcyclopropanes using transition metal catalysis have been developed. Uemura and coworkers [204] were the first to
and coworkers used this chemistry with propargylic acetate 255 to achieve cyclopropanation with various dienes, for example cyclopentadiene, to generate a cis/trans-mixture of divinylcyclopropanes 256. Heating of this mixture of compounds resulted in the formation of bridged tricycle 257 in good yield
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Graphical Abstract
Scheme 1:
Vogel’s first approach towards the divinylcyclopropane rearrangement [4] and characterization of cis-d...