Silver(I) ion catalyzed rearrangements of strained .sigma. bonds. XX. Substituent effects on the generation, structural rearrangement, and deargentation of argento carbonium ions. Kinetic and product study of the silver(I)-catalyzed isomerization of C1-functionalized tricyclo[4.1.0.02.7] heptanes

Abstract

203formed from the nine-membered ring case examined earlier. The products from 10t and its alcohol were the same as for the cis cases except that the ratio of 12c and 12t was approximately reversed. The spectra of the products are listed below. and 905 cm-l; nmr (6, CCla) 5.57 (m, l), 4.91 (d, J = 18 Hz, 11, 4.86 (d, J = 8 Hz. I), 1.2-2.6 (m, 17); massspectrummle 180.151 (calcdmlefor C I~H~~O , 180.151).Dodeca-l,ll-dien-3-one: nmr (6, CCh) 5.5-6.4 (m, 4), 4.7-5.1 (m, 2),2.3-2.6(m, 2), 1.9-2.3 (m, 2),and 1.1-1.8(m, 10).Kinetic Experiments. A series of ampoules were heated in either a fused salt bath maintained by a Bailey Model 124 proportional controller or in an aluminum block oven regulated by a Cole Palmer Model 1300 proportional controller. All runs for 1Oc used the fused salt bath. The runs for 10t used both and it was established that both devices gave the same rate at the same measured temperature, Each sample was hydrolyzed16 and analyzed on columns D and E. The data were treated as before. Acknowledgment.We thank Research C o r p o r a t i o n cis-Cyclodec-5-en-1-one (12c):for Cottrell Research Grant s u p p o r t .cis-Cyclodec-3-en-1-one. Oxidation3 of cis-cyclodec-3-en-1-01 gave a 62% yield of the desired ketone: ir (neat)

Synthesis and Applications of Bicyclo[1.1.0]butyl and Azabicyclo[1.1.0]butyl Organometallics

“…Both methyl iodide [93] and dimethyl sulfate [95] have been employed for the methylation of substituted bicyclo[1.1.0]butanes, although this is typically used to protect a potentially reactive site (Scheme 11). On the other hand, the reaction of lithiated bicyclo[1.1.0]butanes with epoxides has been demonstrated to be an effective way to both alkylate the bridgehead position and to install a highly versatile alcohol handle that can be engaged in subsequent reactions [96–97] …”

“…On the other hand, the reaction of lithiated bicyclo[1.1.0]butanes with epoxides has been demonstrated to be an effective way to both alkylate the bridgehead position and to install a highly versatile alcohol handle that can be engaged in subsequent reactions. [96][97] In an extensive study on the reactivity of 1-(arylsulfonyl)bicyclo[1.1.0]butanes 48, Gaoni and coworkers demonstrated that these electron deficient species display similar reactivity to unsaturated carbonyl compounds. [98] In this regard, it was shown that 48 can act as a Michael/Giese acceptor, allowing the addition of heteroatom-based nucleophiles (49 a-49 e), hydride reductants (49 f), organocopper reagents (49 g-49 i) and nucleophilic radicals (49 j) to the bridgehead carbon (Scheme 12a).…”

“…The coupling of bicyclo[1.1.0]butyl lithium 1 with boronic esters to generate highly strained boronate complexes has been pioneered by Aggarwal and coworkers. The resulting electron rich bicyclo[1.1.0]butyl boronate complexes (97) have been shown to interact with electrophilic Pd(II) complexes, generated from the oxidative addition of a Pd(0) catalyst into an aryl triflate (Scheme 24a). [55] This coordination induces a stereoselective strain-release-promoted 1,2-metallate rearrangement Of relevance to the present review was the observation that no cross-coupling product was formed upon the in situ generation of bicyclo[1.1.0]butyl lithium from dibromo cyclopropane 76 (Scheme 24b).…”

“…The generality of this approach was later established when Aggarwal and coworkers reported the activation of the same bicyclo[1.1.0]butyl boronate complexes (97) with a wide range of electrophiles (Scheme 25a). [120] These included aldehydes, ketones, imines, acyl chlorides, chloroformates, carbon dioxide and even electrophilic sources of chlorine, bromine and iodide to provide alternative cyclobutyl boronic esters (101 a-101 i).…”

“…On the other hand, the reaction of lithiated bicyclo[1.1.0]butanes with epoxides has been demonstrated to be an effective way to both alkylate the bridgehead position and to install a highly versatile alcohol handle that can be engaged in subsequent reactions. [ 96 , 97 ]…”