The use of α-d-glucopyranosides as surrogates for the β-l-glucopyranosides in the stereoselective cyclopropanation reaction

Charette, André B.; Turcotte, Nathalie; Marcoux, Jean-François

doi:10.1016/s0040-4039(00)75825-4

Cited by 30 publications

(5 citation statements)

References 17 publications

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“…This has been examined from the perspective of chiral auxiliary-based diastereoselective methods or enantioselective cyclopropanations using chiral catalysts. Building on the pioneering studies of Mash, Yamamoto, Imai, and Tai, Charette found an effective, covalently attached carbohydrate auxiliary for the cyclopropanation of prochiral cis- and trans- allylic alcohols . Utilizing the directing effect of the hydroxy groups of various 2-hydroxyglucopyranosides 9 on the metal carbenoid, cyclopropanes 10 were produced in nearly quantitative yields and very high diastereoselectivities by reaction with 10 equiv diethylzinc/diiodomethane (Table ).…”

Section: 1 [2 + 1] Cycloadditions Using Stoichiometric Amounts Of Zin...mentioning

confidence: 99%

Transition Metal-Mediated Cycloaddition Reactions

1996

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Contents 1. Introduction 49 2. Three-Membered Ring Formation 50 2.1. [2 + 1] Cycloadditions Using Stoichiometric Amounts of Zinc Carbenoids (Simmons−Smith Type) 50 2.2. [2 + 1] Cycloadditions with Stoichiometric Amounts of Samarium Carbenoids 52 2.3. [2 + 1] Cycloadditions with Transition Metal-Stabilized Alkyl Carbenes of Cu, Pd, Ni, Co, and Rh 52 2.4. Cyclopropanations with Metal Carbenes Derived from R-Diazocarbonyl Compounds 54 2.5. [2 + 1] Cycloadditions with Vinylcarbenes 54 2.6. [2 + 1] Cycloadditions with Palladium Complexes of Oxatrimethylenemethane 56 2.7. Transition Metal-Catalyzed Aziridinations 57 3. Four-Membered Ring Formation 58 3.1. [2 2π + 2 2π ] Cycloadditions of Strained Alkenes with Electron-Deficient Olefins 58 3.2. [2 2π + 2 2π ] Cycloadditions of Strained Alkenes with Acetylenes 59 3.3. Intramolecular [2 2π + 2 2π ] Cycloadditions 60 4. Five-Membered Ring Formation 60 4.1. [3 2σ + 2 2π ] Cycloadditions with Metallacyclobutanes 60 4.2. [3 2σ + 2 2π ] Cycloadditions with Pd−Trimethylenemethane Complexes 61 4.3. Intramolecular [3 2σ + 2 2π ] Cycloadditions with Pd−TMM Complexes 62 4.4. [3 2σ + 2 2π ] Cycloadditions with Methylenecyclopropane 64 4.5. Intramolecular [3 2σ + 2 2π ] Cycloadditions with Methylenecyclopropanes 66 4.6. [3 4π + 2 2π ] Cycloadditions with Metal Carbenoids 67 4.7. [4 4π + 1 2π ] Cycloadditions 69 5. Six-Membered Ring Formation 69 5.1. [2 2π + 2 2π + 2 2π ] Cycloadditions 69 5.2. Acetylene [2 2π + 2 2π + 2 2π ] Cyclotrimerization Reactions 70 5.3. Acetylene−Olefin [2 2π + 2 2π + 2 2π ] Cyclotrimerizations 71 5.4. Hetero [2 2π + 2 2π + 2 2π ] Cyclotrimerizations 72 5.5. Homo-Diels−Alder [2 2π + 2 2π + 2 2π ] Cycloadditions 72 5.6. Bis-Homo-Diels−Alder [2 2π + 2 2π + 2 2π ] Cycloadditions 74 5.7. [3 2π + 3 2σ ] Cycloadditions 74 5.8. [4 4π + 2 2π ] Cycloadditions 75 6. Seven-Membered Ring Formation 78 6.1. [4 4π + 3 2σ ] Cycloadditions 78 6.2. [5 2π+2σ + 2 2π ] Cycloadditions 79 7. Eight-Membered Ring Formation 79 7.1. [2 2π + 2 2π + 2 2π + 2 2π ] Cycloadditions 80 7.2. [4 4π + 2 2π + 2 2π ] Cycloadditions 80 7.3. [4 4π + 4 4π ] Cycloadditions 81 7.4. [6 6π + 2 2π ] Cycloadditions 83 8. Ten-Membered Ring Formation 85 9. Conclusion and Remarks 87 49

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Section: 1 [2 + 1] Cycloadditions Using Stoichiometric Amounts Of Zin...mentioning

confidence: 99%

Transition Metal-Mediated Cycloaddition Reactions

1996

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“…Charette has described a number of useful asymmetric variants of the Simmons−Smith reaction. In the realm of auxiliary-based methods, those using both carbohydrates and enantiomerically pure 1,2- trans -cyclohexanediol as covalent modifiers for allylic alcohols have been fruitful (Scheme , eq 4) …”

Section: Introductionmentioning

confidence: 99%

Catalytic, Enantioselective Cyclopropanation of Allylic Alcohols. Substrate Generality

1997

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Catalytic, enantioselective cyclopropanation of a broad range of allylic alcohols and one homoallylic alcohol was carried out. The cyclopropanation reagent employed was bis(iodomethyl)zinc generated by the method of Furukawa, and the chiral promoter used (10 mol %) was the N,N-bis(methanesulfonyl) derivative of (R,R)-1,2-diaminocyclohexane. Three experimental features were found to be critical for the rapid and selective cyclopropanation: (1) use of the ethylzinc alkoxide of the allylic alcohol as the substrate by prior deprotonation of the allylic alcohols by diethylzinc, (2) the formation of the zinc complex of the promoter by prior deprotonation of the bis-sulfonamide with diethylzinc, and (3) the use of added zinc iodide generated in situ from diethylzinc and iodine. The stereoselectivity of cyclopropanation was found to be independent of olefin geometry and worked well for substrates bearing both aliphatic and aromatic substituents at either or both 3-positions of the allylic alcohol. However, a methyl substituent on the 2-position of the allyl alcohol was not well tolerated and led to slow reactions and poor enantioselectivities. A rationale for the observed selectivities is proposed.

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“…This cyclopropanation reaction had been studied in allyl b-D-glucopyranosides in toluene, which takes place with high diastereoisomeric excesses. 8b, [9][10][11][12] As our products, with a free OH at at the 2-and 3-position of the sugar, are not very soluble in toluene, we decided to use CH 2 Cl 2 as the solvent, and chose for this assay, compounds 3 and 6 (Scheme 4). Compounds 23 and 24 were obtained in 57% and 22% of diastereoisomeric excess, respectively (determined by 1 …”

Section: Resultsmentioning

confidence: 99%

“…7 There are only a few precedents for the stereoselective synthesis of cyclopropanes using carbohydrates as chiral auxiliaries. [8][9][10][11][12] Our group has recently published the stereoselective cyclopropanation (using the diiodomethane/diethyl zinc system) of a wide range of alkenes linked via an acetal function to different backbones of sugar moieties. 13,14 It is important to note that the union of the olefin to the carbohydrate via an acetal function allowed the easy separation of the new chiral cyclopropane fragment and the chiral auxiliary by mild acid hydrolysis.…”

Section: Introductionmentioning

confidence: 99%