Stereoinversion of Unactivated Alcohols by Tethered Sulfonamides

Marcyk, Paul T.; Jefferies, Latisha R.; AbuSalim, Deyaa I.; Pink, Maren; Baik, Mu‐Hyun; Cook, Silas P.

doi:10.1002/anie.201812894

Cited by 50 publications

(37 citation statements)

References 54 publications

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“…Despite these recent advances emphasized above, there are no reported methods on either the synthesis of non-allylic six-membered heterocyclic compounds through intramolecular substitution of the OH group or the direct intramolecular substitution of tertiary alcohols with chirality transfers, or the use of substrates containing weak nucleophiles (such as phenolic OH) 28 . In order to offer a synthetic route to overcome these limitations, we continued our efforts on acid-catalyzed transformations and report herein a Fe(OTf) 3 -catalyzed intramolecular substitution of enantioenriched secondary and tertiary alcohols by N- , O- and S- centered nucleophiles with high degree of chirality transfer.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular substitutions of secondary and tertiary alcohols with chirality transfer by an iron(III) catalyst

et al. 2019

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Optically pure alcohols are abundant in nature and attractive as feedstock for organic synthesis but challenging for further transformation using atom efficient and sustainable methodologies, particularly when there is a desire to conserve the chirality. Usually, substitution of the OH group of stereogenic alcohols with conservation of chirality requires derivatization as part of a complex, stoichiometric procedure. We herein demonstrate that a simple, inexpensive, and environmentally benign iron(III) catalyst promotes the direct intramolecular substitution of enantiomerically enriched secondary and tertiary alcohols with O -, N -, and S -centered nucleophiles to generate valuable 5-membered, 6-membered and aryl-fused 6-membered heterocyclic compounds with chirality transfer and water as the only byproduct. The power of the methodology is demonstrated in the total synthesis of (+)-lentiginosine from D-glucose where iron-catalysis is used in a key step. Adoption of this methodology will contribute towards the transition to sustainable and bio-based processes in the pharmaceutical and agrochemical industries.

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Section: Introductionmentioning

confidence: 99%

Intramolecular substitutions of secondary and tertiary alcohols with chirality transfer by an iron(III) catalyst

et al. 2019

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“…A conceptually different approach to catalytic nucleophilic substitution termed "borrowing hydrogen" (16)(17)(18) involves oxidation of the alcohol, condensation with a nucleophile, and then reduction to achieve the product of a direct substitution reaction. Despite these advances, the development of catalytic methods that enable stereospecific bimolecular substitution of nonactivated chiral alcohols remains a major challenge (19,20). Although some progress has been made by using cyclopropenone catalysis (21), most effort to date has been focused on modifying the original Mitsunobu protocol by redox recycling of the stoichiometric reagents.…”

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confidence: 99%

Redox-neutral organocatalytic Mitsunobu reactions

Beddoe

Andrews

Magné

et al. 2019

Science

162

115

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Nucleophilic substitution reactions of alcohols are among the most fundamental and strategically important transformations in organic chemistry. For over half a century, these reactions have been achieved by using stoichiometric, and often hazardous, reagents to activate the otherwise unreactive alcohols. Here, we demonstrate that a specially designed phosphine oxide promotes nucleophilic substitution reactions of primary and secondary alcohols in a redox-neutral catalysis manifold that produces water as the sole by-product. The scope of the catalytic coupling process encompasses a range of acidic pronucleophiles that allow stereospecific construction of carbon-oxygen and carbon-nitrogen bonds.

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“…Enantiopure chiral substrates were also used by Baik, Cook and co-workers to develop iron(III)-catalyzed stereospecific nucleophilic substitutions [ 77 ]. Preliminary studies on intermolecular amination reactions of secondary and tertiary alcohols demonstrated the efficiency of iron catalysts, which afforded the corresponding desired products in high yields.…”

Section: Othersmentioning

confidence: 99%

Recent Advances in Asymmetric Iron Catalysis

2020

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Asymmetric transition-metal catalysis represents a fascinating challenge in the field of organic chemistry research. Since seminal advances in the late 60s, which were finally recognized by the Nobel Prize to Noyori, Sharpless and Knowles in 2001, the scientific community explored several approaches to emulate nature in producing chiral organic molecules. In a scenario that has been for a long time dominated by the use of late-transition metals (TM) catalysts, the use of 3d-TMs and particularly iron has found, recently, a widespread application. Indeed, the low toxicity and the earth-abundancy of iron, along with its chemical versatility, allowed for the development of unprecedented and more sustainable catalytic transformations. While several competent reviews tried to provide a complete picture of the astounding advances achieved in this area, within this review we aimed to survey the latest achievements and new concepts brought in the field of enantioselective iron-catalyzed transformations.

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Stereoinversion of Unactivated Alcohols by Tethered Sulfonamides

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 50 publications

References 54 publications

Intramolecular substitutions of secondary and tertiary alcohols with chirality transfer by an iron(III) catalyst

Intramolecular substitutions of secondary and tertiary alcohols with chirality transfer by an iron(III) catalyst

Redox-neutral organocatalytic Mitsunobu reactions

Recent Advances in Asymmetric Iron Catalysis

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