Catalytic C–H Bond Functionalization of Cyclopropane Derivatives

Roman, Daniela Sustac; Charette, André B.

doi:10.1007/3418_2015_118

Cited by 11 publications

(8 citation statements)

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“…This structural flexibility is remarkable since very often the precise tether length of the directing group is found to be crucial for reactivity in C–H activation . A further point to note is that, compared to the plethora of methods for the construction of five- or six-membered N -heterocyclic systems, there are very few reports on the direct synthesis of seven-membered rings by Pd-catalyzed oxidative cyclization …”

Section: Results and Discussionmentioning

confidence: 99%

Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp³)–H Activation: Late-Stage Diversification of Amino Acids and Peptides

et al. 2016

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Esta es la versión de autor del artículo publicado en: This is an author produced version of a paper published in: El acceso a la versión del editor puede requerir la suscripción del recurso Access to the published version may require subscription Mo(CO) 6 from 1.0 equiv (43% conversion, entry 1 in Table 149 1) to 0.5 equiv (67% conversion, entry 2 in 199 This good trans-diastereoselectivity is remarkable, revealing a 200 marked preference for C−H activation of the pro-S methyl 201 group of (+)-3.23e Importantly, the major (−)-trans-9 202 diastereomer could be isolated in 75% yield with no appreciable 203 loss of enantiopurity (97% ee) upon standard chromatography. 204Although the structure of the bimetallic complex of γ-205 cyclopalladation of tert-leucine derivative (+)-1 (complex A) 206 strongly suggested that the NH−SO 2 Py directing group is 207 crucial for this transformation, we were interested in confirming 208 this issue by screening other potentially coordinating N-209 protecting groups. For this purpose, a set of L-valine derivatives 210 (substrates 4−8) were examined in the carbonylation reaction 211 under the optimized conditions, and the results are summarized 212 in Table 2. While L-valine methyl ester hydrochloride 213 decomposed under the reaction conditions (entry 2 in Table 214 2), the NH-Ts derivative 5 and the NH-(2-thienyl)sulfonyl 215 derivative 6 were recovered unaltered without detecting any 216 carbonylation product (entries 3 and 4, respectively, in Table 217 2). The reaction of the (8-quinolyl)sulfonyl and (2-pyridyl)-218 carbonyl derivatives (7 and 8, respectively) led to a complex 219 mixture of products in low conversion (<10%) (entries 5 and 6 220 in Table 2). Interestingly, the lack of reaction efficiency 87 (75) e 5.7:1 (9) 9 7 2 −(4)a Reaction conditions are identical to those given in Table 1 This method was extended to β-amino acid derivatives, as 260 exemplified by the clean cyclocarbonylation of β-amino ester 261 (±)-19, affording the product (±)-20 as a separable 3.8:1 262 mixture of trans/cis diastereoisomers in good overall yield 263 (76%). 264Extension of the Method to Simple Aliphatic Amines. 265 The broad substrate scope displayed by this reaction with α-266 amino acid derivatives prompted us to explore the extension of 267 this method to simple aliphatic amine derivatives. We first 268 tested if compound (−)-21, analogue to tert-leucine derivative 269 1 but lacking the methyl ester moiety, could undergo γ-270 cyclometalation. The stoichiometric reaction of (−)-21 with 271 Pd(OAc) 2 (1.0 equiv) in acetonitrile at 60°C for 3.5 h, cleanly 272 provided, after simple recrystallization, the expected bimetallic 273 complex B in 91% yield (unambiguously determined by singles3 274 crystal X-ray diffraction (XRD) analysis; see Scheme 3), which 275 presents an analogous structure to complex A. This result demonstrated that the ester group at the α-277 position of the previously studied α-amino ester derivatives was 278 not essential for the C−H activation step. Fu...

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Section: Results and Discussionmentioning

confidence: 99%

Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp³)–H Activation: Late-Stage Diversification of Amino Acids and Peptides

et al. 2016

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“…In order to perform a direct C–H functionalization on cyclopropanes, palladium catalysis with fine-tuned directing groups has been most successful. 5 a , b However, the regioselectivity could not be controlled when several benzylic C–H bonds were present in ortho position. 5 c In particular, 1,1-aryl-alkynyl cyclopropanes are useful building blocks in synthetic and medicinal chemistry.…”

Section: Introductionmentioning

confidence: 99%

Substrate-controlled C–H or C–C alkynylation of cyclopropanes: generation of aryl radical cations by direct light activation of hypervalent iodine reagents

2022

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“…Because of the high propensity of cyclopropanols toward these and other ring opening modes, it is difficult to install a new functional group into existing cyclopropanols without rupture of the three-membered ring. This marks a sharp contrast with the extensive development of C–H activation of other types of cyclopropanes containing directing groups …”

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Zinc-Catalyzed β-Functionalization of Cyclopropanols via Enolized Homoenolate

Sekiguchi

Yoshikai

2021

J. Am. Chem. Soc.

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We report herein a zinc-catalyzed β-allylation of cyclopropanols with Morita–Baylis–Hillman (MBH) carbonates with retention of the cyclopropane ring. The reaction is promoted by a zinc aminoalkoxide catalyst, affording cyclopropyl-fused α-alkylidene-δ-valerolactone derivatives in moderate to good yields. Mechanistic experiments suggest that the present reaction does not proceed via direct β-C–H cleavage of the cyclopropanol, but involves zinc homoenolate and its enolization to generate a key bis-nucleophilic species. α-Allylation of this “enolized homoenolate” with MBH carbonate would be followed by regeneration of the cyclopropane ring and irreversible lactonization. The enolized homoenolate mechanism has also been proven to allow for β-functionalization with alkylidenemalononitrile as the reaction partner. A sequence of the present reaction and known cyclopropanol transformation provides an opportunity to transform a simple cyclopropanol into α,β- or β,β-difunctionalized ketones.

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Catalytic C–H Bond Functionalization of Cyclopropane Derivatives

Cited by 11 publications

References 63 publications

Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp³)–H Activation: Late-Stage Diversification of Amino Acids and Peptides

Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp³)–H Activation: Late-Stage Diversification of Amino Acids and Peptides

Substrate-controlled C–H or C–C alkynylation of cyclopropanes: generation of aryl radical cations by direct light activation of hypervalent iodine reagents

Zinc-Catalyzed β-Functionalization of Cyclopropanols via Enolized Homoenolate

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Catalytic C–H Bond Functionalization of Cyclopropane Derivatives

Cited by 11 publications

References 63 publications

Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp3)–H Activation: Late-Stage Diversification of Amino Acids and Peptides

Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp3)–H Activation: Late-Stage Diversification of Amino Acids and Peptides

Substrate-controlled C–H or C–C alkynylation of cyclopropanes: generation of aryl radical cations by direct light activation of hypervalent iodine reagents

Zinc-Catalyzed β-Functionalization of Cyclopropanols via Enolized Homoenolate

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Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp³)–H Activation: Late-Stage Diversification of Amino Acids and Peptides

Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp³)–H Activation: Late-Stage Diversification of Amino Acids and Peptides