Carbenoids with neighboring heteroatoms. VI. Electrophilic reactions of .alpha.-chlorocyclopropyllithium compounds which are epimeric at the carbenoid center
“…A first example of such a reaction supporting the S N 2-type anti stereochemistry was shown in Scheme ; see the transformations 58 → 59 → 60 . Another example of stereoselectivity in carbenoid C−H insertion reactions was provided by Taylor; ,6i,6m see Scheme . 13 Different Reactivity of the Two Diastereomeric Li/Cl Carbenoids 61 and 65…”
Section: 23 Reaction With C−h Bondsmentioning
confidence: 99%
“…Reaction of the diastereomeric carbenoid 43 is much slower, giving the two products 42 and 45 (the different behavior of 40 and 43 also rules out the reaction of carbenes). Compound 45 should be formed in a concerted, S N 2-type pathway via [44] ‡ , which however is not stabilized by a Lewis base-Li + interaction as is the case for [41] ‡ . Compound 42 could be formed via a transition state analogous to [36] ‡ in Scheme 8.…”
“…A first example of such a reaction supporting the S N 2-type anti stereochemistry was shown in Scheme ; see the transformations 58 → 59 → 60 . Another example of stereoselectivity in carbenoid C−H insertion reactions was provided by Taylor; ,6i,6m see Scheme . 13 Different Reactivity of the Two Diastereomeric Li/Cl Carbenoids 61 and 65…”
Section: 23 Reaction With C−h Bondsmentioning
confidence: 99%
“…Reaction of the diastereomeric carbenoid 43 is much slower, giving the two products 42 and 45 (the different behavior of 40 and 43 also rules out the reaction of carbenes). Compound 45 should be formed in a concerted, S N 2-type pathway via [44] ‡ , which however is not stabilized by a Lewis base-Li + interaction as is the case for [41] ‡ . Compound 42 could be formed via a transition state analogous to [36] ‡ in Scheme 8.…”
“…The reactivity of metal carbenoids is dependent on the types of metals (Li, Na, Mg, Cu, and Zn) and halogen atoms (Cl, Br, and I) on the carbenoid carbon atom, and the stereochemistry of substrates markedly affects the outcome of the reaction . These experimental results indicate that the C–H insertion does not occur via free carbenes, and that the condition of the C–H bond position (backside of a leaving group) is essential for successful C–H insertion.…”
“…Caled for C13H17NO2: C, 60.48; H, 6.64; N, 5.43. Found: C, 60.46; H, 6.59; N, 5.45. 6-trans-Styryl-3-azabicyclo[3.1.0]hexane (9). A butyllithium solution (18.9 mL of 2.4 M hexane solution, 0.045 mol) was added dropwise to a stirred solution of 6-exo-chloro-3-phenethyl-3-azabicyclo[3.1.0]hexane (6) (5.0 g, 0.023 mol) in 100 mL of ethyl ether under a nitrogen atmosphere.…”
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