Cyclopropenone Catalyzed Substitution of Alcohols with Mesylate Ion

Nacsa, Eric D.; Lambert, Tristan H.

doi:10.1021/ol302970c

Cited by 58 publications

(32 citation statements)

References 38 publications

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“…nones ( 3), have also been shown to effectively activate alcohols for mesylate displacements( Scheme 1B). [6] Finally,L ewis and Brønsted acids can be used to activate alcoholsf or intramolecular cyclization to the corresponding oxa-, aza-, andt hiacycles( Scheme 1C). [7] Despite these important advances in phosphine-free methods, they require multiple steps and elevated temperatures (Scheme1A),o rl ack the nucleophile scope of phosphine-basedMitsunobu protocols (Scheme 1B,C).…”

mentioning

confidence: 99%

One‐Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride

Epifanov

Hodgson

et al. 2020

Chemistry A European J

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The Mitsunobu reaction is ap owerful transformation for the one-pota ctivation and substitution of aliphatic alcohols. Significant efforts have focused on modifying the classic conditions to overcome problems associated with purification from phosphine-based byproducts. Herein,w er eport ap hosphine free methodf or alcohola ctivationand substitution that is mediated by sulfuryl fluoride. This new method is effective for aw ide range of primary alcohols using phthalimide, di-tert-butyl-iminodicarboxylate, and aromatict hiol nucleophilesi n7 4% average yield. Activatedc arbon nucleophilesa nd ad eactivated phenolw ere also effective for this reaction in good yields. Secondary alcohols were also successful substrates using aryl thiols, affording the corresponding sulfides in 56 % averagey ield with enantiomeric ratios up to 99:1. This new protocol has ad istinct synthetic advantage over many existing phosphine-based methods as the byproducts are readily separable. Thisf eature was exploitedi n severale xamples that did not require chromatographyf or purification. Furthermore, the mild reaction conditions enabled further in situ derivatization for the one-pot conversion of alcohols to amines or sulfones. This methoda lso provides ab oarder nucleophile scope comparedt oe xisting phosphine-free methods.

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mentioning

confidence: 99%

One‐Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride

Epifanov

Hodgson

et al. 2020

Chemistry A European J

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“…Benzyl 6‐Bromohexyl Ether (7a‐Bn): Following GP‐2, 3 (10.2 mg, 30 µmol) was added to a mixture of 6a (40.8 µL, 0.300 mmol), ATTACK‐Bn (107.8 mg, 0.360 mmol), and molecular sieves 5 Å (37.5 mg) in 1,4‐dioxane (1.2 mL). After 3.5 h, the reaction mixture was diluted with EtOAc (50 mL) and filtered.…”

Section: Methodsmentioning

confidence: 99%

Preparation of Alkyl Ethers with Diallyltriazinedione‐Type Alkylating Agents (ATTACKs‐R) Under Acid Catalysis

et al. 2019

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Diallyltriazinedione‐type acid‐catalyzed alkylating agents (ATTACKs‐R) with 10 different alkyl groups (R), including benzyl, substituted benzyl, allyl, and methyl groups were synthesized. The palladium‐catalyzed intramolecular O‐to‐N allylic rearrangement of 2,4‐bis(allyloxy)‐6‐chloro‐1,3,5‐triazine was developed to introduce various alkoxy groups into the N,N′‐dialkylated triazinedione skeleton. O‐Alkylation of alcohols with ATTACKs‐R was carried out in 1,4‐dioxane in the presence of 2,6‐di‐tert‐butylpyridinium trifluoromethanesulfonate or trifluoromethanesulfonic acid as a catalyst. Six selected ATTACKs‐R bearing benzylic R groups were employed to prepare alkyl ethers from primary, secondary, and tertiary alcohols. The reactions of ATTACKs‐R bearing an o‐nitro‐substituted benzyl group tended to afford low yields. Comparison of four different triazinedione‐based benzylating reagents suggested that the N,N′‐substituents affected the reactivity.

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“…In 2012, Nacsa and Lambert devised an alternative synthetic pathway to the Mitsunobu reaction (Scheme 17) by using acatalytic cyclopropenium activation to promote the mesylation of alcohols with inversion of the configuration. [43] Scheme 15. Dehydrativeglycosylation reactions promoted by cyclopropenium ions.…”

Section: Angewandte Chemiementioning

confidence: 99%

Promotion of Organic Reactions by Non‐Benzenoid Carbocyclic Aromatic Ions

et al. 2016

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The first three primary members of the non-benzenoid carbocyclic aromatic ion family, namely cyclopropenium, cyclopentadienide, and cycloheptatrienium (tropylium) ions, have planar cyclic structures with (4n+2)π electrons in fully conjugated systems. They fulfill Hückel's rule for aromaticity and hence possess extraordinary stability. Since the historic discovery of tropylium bromide in the late 19th Century, these non-benzenoid aromatic ions have attracted a lot of attention because of their unique combination of stability and reactivity. The charge on the aromatic ions makes them more prone to nucleophilic/electrophilic reactions than the neutral benzenoid counterparts. Within the last seven years, there has been a large number of investigations in utilizing aromatic ions to mediate organic reactions. This Review highlights these recent developments and discusses the potential of aromatic ions in promoting synthetically useful organic transformations.

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Cyclopropenone Catalyzed Substitution of Alcohols with Mesylate Ion

Cited by 58 publications

References 38 publications

One‐Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride

One‐Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride

Preparation of Alkyl Ethers with Diallyltriazinedione‐Type Alkylating Agents (ATTACKs‐R) Under Acid Catalysis

Promotion of Organic Reactions by Non‐Benzenoid Carbocyclic Aromatic Ions

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