Osmium-Catalyzed Vicinal Oxyamination of Alkenes by <i>N</i>-(4-Toluenesulfonyloxy)carbamates

Masruri,; Willis, Anthony C.; McLeod, Malcolm D.

doi:10.1021/jo301372y

Cited by 42 publications

(31 citation statements)

References 69 publications

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“…4,[9][10][11][12] High regioselectivity in the oxyamination reaction would significantly simplify product analysis of the diastereomeric mixtures. In the absence of ligand control, the intermolecular oxyamination of unsymmetrically substituted alkenes by pre-formed nitrogen sources typically gives high selectivity for products where the nitrogen adds to the less substituted end of the double bond.…”

Section: Resultsmentioning

confidence: 99%

“…12 This involved reaction of the allylic alcohol or its derivative (1.0 equiv) and benzyl N-(4tosyloxy)carbamate 1 (1.2 equiv) with potassium osmate dihydrate (0.04 equiv) in acetonitrile/water (3:1). 12 This involved reaction of the allylic alcohol or its derivative (1.0 equiv) and benzyl N-(4tosyloxy)carbamate 1 (1.2 equiv) with potassium osmate dihydrate (0.04 equiv) in acetonitrile/water (3:1).…”

Section: Resultsmentioning

confidence: 99%

“…12 General Procedure 1 for the Osmium-Catalyzed Oxyamination Reaction 12 General Procedure 1 for the Osmium-Catalyzed Oxyamination Reaction…”

Section: Methodsmentioning

confidence: 99%

“…3,4 The recent development of pre-formed nitrogen sources has improved the efficiency, chemoselectivity and control of the osmiumcatalyzed oxyamination reaction. The development of nontethered pre-formed nitrogen sources has further expanded the scope of this process, [9][10][11][12] and includes the introduction of N-(4-chlorobenzoyloxy)carbamates which allow for the enantioselective intermolecular oxyamination of mono-and di-substituted alkenes in the presence of cinchona alkaloidderived chiral ligands. The development of nontethered pre-formed nitrogen sources has further expanded the scope of this process, [9][10][11][12] and includes the introduction of N-(4-chlorobenzoyloxy)carbamates which allow for the enantioselective intermolecular oxyamination of mono-and di-substituted alkenes in the presence of cinchona alkaloidderived chiral ligands.…”

Section: Introductionmentioning

confidence: 99%

“…The development of nontethered pre-formed nitrogen sources has further expanded the scope of this process, [9][10][11][12] and includes the introduction of N-(4-chlorobenzoyloxy)carbamates which allow for the enantioselective intermolecular oxyamination of mono-and di-substituted alkenes in the presence of cinchona alkaloidderived chiral ligands. 12 The reactions occur with low catalyst loadings and afford good regioselectivity for unsymmetrically substituted alkenes. 12 The reactions occur with low catalyst loadings and afford good regioselectivity for unsymmetrically substituted alkenes.…”

Section: Introductionmentioning

confidence: 99%

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Diastereoselective Osmium‐catalyzed Vicinal Oxyamination of Acyclic Allylic Alcohol Derivatives

2013

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The osmium-catalyzed oxyamination of chiral acyclic allylic alcohol derivatives bearing mono- and 1,1-di-substituted double bonds with benzyl N-(4-tosyloxy)carbamate proceeds with high regioselectivity and moderate levels of diastereoselectivity favoring the anti product. The observed stereoselectivity shows a clear and systematic trend with anti:syn ratios increasing in line with the size of substituent at both the allylic stereocenter and double bond α-carbon. The stereoinduction is in accord with the sense of diastereoselectivity predicted by Kishi's empirical rule and a previously reported transition state model for the osmium-catalyzed dihydroxylation of allylic alcohol derivatives. In contrast, allylic alcohol derivatives bearing trisubstituted double bonds show low or no reactivity in the oxyamination reaction affording the syn product in low yield in the cases examined.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…12 General Procedure 1 for the Osmium-Catalyzed Oxyamination Reaction 12 General Procedure 1 for the Osmium-Catalyzed Oxyamination Reaction…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Diastereoselective Osmium‐catalyzed Vicinal Oxyamination of Acyclic Allylic Alcohol Derivatives

2013

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N-Boc-O-tosylhydroxylamine

Lattanzi

2014

Encyclopedia of Reagents for Organic Synthesis

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Transition‐Metal‐Catalyzed Aminooxygenation of Alkenes

Chemler¹,

Chen²,

Karyakarte³

et al. 2021

Organic Reactions

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Alkene aminooxygenation reactions provide vicinal amino alcohol derivatives, moieties that frequently appear in catalysts, drugs, and other valuable molecules. This Chapter reviews transition‐metal‐catalyzed aminooxygenations of alkenes and aims to serve as a guide in the selection of appropriate reagents and procedures for specific substrate classes and desired transformations. Inter‐ and intramolecular aminooxygenation reactions catalyzed by osmium, palladium, platinum, gold, copper, iron, iridium, rhodium, ruthenium, and manganese are presented, as is a discussion of the factors involved in reactivity and selectivity. A brief section on non‐metal catalyzed alkene aminohydroxylation is also included. A complete set of alkene aminooxygenation reactions through mid‐2020 is provided in the Tabular Survey.

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Osmium-Catalyzed Vicinal Oxyamination of Alkenes by N-(4-Toluenesulfonyloxy)carbamates

Cited by 42 publications

References 69 publications

Diastereoselective Osmium‐catalyzed Vicinal Oxyamination of Acyclic Allylic Alcohol Derivatives

Diastereoselective Osmium‐catalyzed Vicinal Oxyamination of Acyclic Allylic Alcohol Derivatives

N-Boc-O-tosylhydroxylamine

Transition‐Metal‐Catalyzed Aminooxygenation of Alkenes

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