Site‐Selective Oxidation of Unactivated CH Bonds with Hypervalent Iodine(III) Reagents

Moteki, Shin A.; Usui, Asuka; Zhang, Tiexin; Solorio‐Alvarado, César R.; Maruoka, Keiji

doi:10.1002/anie.201304359

Cited by 71 publications

(57 citation statements)

References 37 publications

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“…As comparison, the C–H chlorination of norbornane with common reagents (e.g., Cl 2 or SO 2 Cl 2 ) leads to mixtures of the exo and endo isomers. 11 Both trans - and cis -1,2-dimethyl cyclohexanes– benchmark substrates for sterically-selective aliphatic C– H functionalizations 13 –exhibited excellent methylene selectivity (entries 10 and 11). Adamantane C–H chlorination involving chlorine free radical is documented to be a poorly selective process, with k t / k s = 3.5.…”

Section: Development Of the Aliphatic C–h Chlorinationmentioning

confidence: 99%

Site-Selective Aliphatic C–H Chlorination Using N-Chloroamides Enables a Synthesis of Chlorolissoclimide

et al. 2016

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Methods for the practical, intermolecular functionalization of aliphatic C–H bonds remain a paramount goal of organic synthesis. Free radical alkane chlorination is an important industrial process for the production of small molecule chloroalkanes from simple hydrocarbons, yet applications to fine chemical synthesis are rare. Herein, we report a site-selective chlorination of aliphatic C–H bonds using readily available N-chloroamides, and apply this transformation to a synthesis of chlorolissoclimide, a potently cytotoxic labdane diterpenoid. These reactions deliver alkyl chlorides in useful chemical yields with substrate as the limiting reagent. Notably, this approach tolerates substrate unsaturation that poses major challenges in chemoselective, aliphatic C–H functionalization. The sterically- and electronically-dictated site selectivities of the C–H chlorination are among the most selective alkane functionalizations known, providing a unique tool for chemical synthesis. The short synthesis of chlorolissoclimide features a high yielding, gram-scale radical C–H chlorination of sclareolide and a three-step/two-pot process for the introduction of the β-hydroxysuccinimide that is salient to all the lissoclimides and haterumaimides. Preliminary assays indicate that chlorolissoclimide and analogues are moderately active against aggressive melanoma and prostate cancer cell lines.

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Section: Development Of the Aliphatic C–h Chlorinationmentioning

confidence: 99%

Site-Selective Aliphatic C–H Chlorination Using N-Chloroamides Enables a Synthesis of Chlorolissoclimide

et al. 2016

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“…[3] To date,an allylcobalt system is ar are example of ah omogenous arene hydrogenation catalyst with excellent cis selectivity (> 95 %), however it undergoes rapid deactivation with < 15 %c onversions achieved. [5][6][7][8] Single-site,m olecule-derived supported catalysts have attracted interest due to their hybrid character combining the complementary features of traditional hetero-and homogeneous systems. Owing to the versatility of alcohols and ketones as synthetic intermediates,t hese products can then be modified in many ways to afford avariety of valuable substances.…”

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confidence: 99%

Single‐Face/All‐cis Arene Hydrogenation by a Supported Single‐Site d⁰ Organozirconium Catalyst

et al. 2016

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The single-site supported organozirconium catalyst Cp*ZrBz2 /ZrS (Cp*=Me5 C5 , Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single-face/all-cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all-cis-cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H2 delivery to a single catalyst-bound arene face, versus any competing intramolecular arene π-face interchange.

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“…[2,6] To address this challenge, superacid solvents, such as H 2 SO 4 , have been used to facilitate anion ligand dissociation and alkane coordination. [2] We have recently reported that main-group electrophilic salts with filled d orbitals (d 10 ) such as Tl III (TFA) 3 and Pb IV (TFA) 4 (TFA = trifluoroacetate) promote efficient and selective stoichiometric CH activation and functionalization of methane (MeH), ethane (EtH), and propane (PrH) in more practical weaker acid solvents (HOAc, HTFA). [2] We have recently reported that main-group electrophilic salts with filled d orbitals (d 10 ) such as Tl III (TFA) 3 and Pb IV (TFA) 4 (TFA = trifluoroacetate) promote efficient and selective stoichiometric CH activation and functionalization of methane (MeH), ethane (EtH), and propane (PrH) in more practical weaker acid solvents (HOAc, HTFA).…”

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confidence: 99%

Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex

et al. 2014

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Direct partial oxidation of methane, ethane, and propane to their respective trifluoroacetate esters is achieved by a homogeneous hypervalent iodine(III) complex in non-superacidic (trifluoroacetic acid) solvent. The reaction is highly selective for ester formation (>99%). In the case of ethane, greater than 0.5 M EtTFA can be achieved. Preliminary kinetic analysis and density functional calculations support a nonradical electrophilic CH activation and iodine alkyl functionalization mechanism.

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Site‐Selective Oxidation of Unactivated CH Bonds with Hypervalent Iodine(III) Reagents

Abstract: Scheme 2. Proposed pathway for the formation of iodanyl radical. Scheme 3. Oxidation of methyl valerate with 2 and 3 d.Scheme 4. Hypervalent iodine(III) reagents 3. [12] naph = naphthalene.

Cited by 71 publications

References 37 publications

Site-Selective Aliphatic C–H Chlorination Using N-Chloroamides Enables a Synthesis of Chlorolissoclimide

Site-Selective Aliphatic C–H Chlorination Using N-Chloroamides Enables a Synthesis of Chlorolissoclimide

Single‐Face/All‐cis Arene Hydrogenation by a Supported Single‐Site d⁰ Organozirconium Catalyst

Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex

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Site‐Selective Oxidation of Unactivated CH Bonds with Hypervalent Iodine(III) Reagents

Abstract: Scheme 2. Proposed pathway for the formation of iodanyl radical. Scheme 3. Oxidation of methyl valerate with 2 and 3 d.Scheme 4. Hypervalent iodine(III) reagents 3. [12] naph = naphthalene.

Cited by 71 publications

References 37 publications

Site-Selective Aliphatic C–H Chlorination Using N-Chloroamides Enables a Synthesis of Chlorolissoclimide

Site-Selective Aliphatic C–H Chlorination Using N-Chloroamides Enables a Synthesis of Chlorolissoclimide

Single‐Face/All‐cis Arene Hydrogenation by a Supported Single‐Site d0 Organozirconium Catalyst

Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex

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Single‐Face/All‐cis Arene Hydrogenation by a Supported Single‐Site d⁰ Organozirconium Catalyst