Silyl-substituted cyclopropanes as versatile synthetic reagents

Paquette, Leo A.

doi:10.1021/cr00075a001

Cited by 120 publications

(26 citation statements)

References 48 publications

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“…Surprisingly, in contrast to the very quick noncatalyzed reaction (eq 1), the hydrostannation of 1a catalyzed by ruthenium, platinum, rhodium, and nickel complexes proceeded very sluggishly, affording moderate to good yields of products, albeit with good facial selectivity (Table 1, entries [1][2][3][4]. Most Pd(0) and Pd(II) catalysts showed high reaction rates, although the yields and selectivity were disappointingly low (Table 1, entries 6-11), attributed to the poor stability of cyclopropenes in the presence of Pd complexes, which are well-known to cause ring-opening, 20 oligomerization, 21 or polymerization 22 of the strained substrates.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, silastannation of all 3,3-disubstituted cyclopropenes proceeded uneventfully, affording the corresponding tetrasubstituted cyclopropanes as sole reaction products in good to very high yields (Table 8, entries [1][2][3][4]. Furthermore, 1,3-disubstituted cyclopropenes 1v-x, possessing an unsymmetrically substituted double bond, underwent an efficient and highly regioselective silastannation producing tetrasubstituted cyclopropanes 12vc-xc, in which the silyl group was attached to the least hindered site ( …”

Section: Sila-and Stannastannation Of Cyclopropenesmentioning

confidence: 99%

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Highly Diastereo- and Regioselective Transition Metal-Catalyzed Additions of Metal Hydrides and Bimetallic Species to Cyclopropenes: Easy Access to Multisubstituted Cyclopropanes

et al. 2007

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The first highly efficient, diastereo- and regioselective transition metal-catalyzed addition of metal hydrides (stannanes, silanes, and germanes) and bimetallic species (ditins and silyltins) to cyclopropenes has been developed. It was shown that the addition across the double bond of cyclopropenes is generally controlled by steric factors and proceeds from the least hindered face. This methodology represents a powerful and atom-economic approach toward a wide variety of highly substituted stereodefined cyclopropylmetals, useful building blocks unavailable by other methods.

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Section: Resultsmentioning

confidence: 99%

Section: Sila-and Stannastannation Of Cyclopropenesmentioning

confidence: 99%

Highly Diastereo- and Regioselective Transition Metal-Catalyzed Additions of Metal Hydrides and Bimetallic Species to Cyclopropenes: Easy Access to Multisubstituted Cyclopropanes

et al. 2007

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“…[76] The base-mediated elimination of TMSOH (Peterson elimination) of silyl-substituted cyclopropanes is among the most used and convenient methods for the synthesis of methylene-and alkylidenecyclopropanes. [77] On the basis that a difluorocyclopropyl anion can be easily generated upon treating a trimethylsilylated difluorocyclopropane with TBAF, Taguchi et al have developed an alternative method for the preparation of methylenedifluorocyclopropanes through the cyclopropyl anion-promoted b-elimination. [78] With alkyl-substituted substrates 98a-c, the expected methylenedifluorocyclopropanes 99a-c were obtained in good yields when an ester group such as a benzoate was a leaving group (Scheme 32).…”

Section: Eliminations Of Xy Groupsmentioning

confidence: 99%

Synthesis of Methylene‐ and Alkylidenecyclopropane Derivatives

Audran

Pellissier

2010

Adv Synth Catal

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Since the methylenecyclopropane moiety is found in many biologically active natural substances, the synthesis of methylene-and alkylidenecyclopropanes remains a considerable challenge. In addition, an attractive feature is their surprising stability, accompanied by a high level of strain, conferring on them an otherwise unattainable chemical reactivity. The growing interest in the chemistry of these compounds has in its turn stimulated the development of alternative approaches to their skeleton, aimed at selectively introducing structural and chemical diversification. The three principal methods to synthesize these important compounds are based on the formation of the cyclopropane ring, the use of preformed cyclopropanes, and the use of preformed methyleneand alkylidenecyclopropanes.

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“…The metal salt-catalyzed [3, [42][43][44] and photochemical [45] reactions of TMSCHN2 with olefins produce the silylcyclopropanes 29 and 30, which are highly versatile synthetic reagents [46] via silylcarbenes or carbenoids as intermediates (Eq. (23)).…”

Section: Preparation Of Silylcyclopropanesmentioning

confidence: 99%