Recent Developments in Metal‐Catalyzed Dihydroxylation of Alkenes

Tse, Man Kin; Schröder, Kristin; Beller, Matthias

doi:10.1002/9783527632039.ch1

Cited by 10 publications

(9 citation statements)

References 159 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To reduce the amount of OsO 4, which is expensive and highly toxic, it is usually used in catalytic amounts of less than 1 mol % together with co-oxidants like N-methylmorpholine N-oxide (NMO). [20] As a small-sized molecule OsO 4 should diffuse with a similar rate like DMDO. Whereas postsynthetic epoxidation is surprisingly fast (reaction half-life: 80 min), [15] the dihydroxylation is significantly slower.…”

Section: Resultsmentioning

confidence: 99%

“…Because of these properties OsO 4 is a promising reagent for the postsynthetic oxidation of MOFs. To reduce the amount of OsO 4, which is expensive and highly toxic, it is usually used in catalytic amounts of less than 1 mol % together with co‐oxidants like N ‐methylmorpholine N ‐oxide (NMO) 20. As a small‐sized molecule OsO 4 should diffuse with a similar rate like DMDO.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Functionalization of Metal–Organic Frameworks through the Postsynthetic Transformation of Olefin Side Groups

Hindelang

Kronast

Vagin

et al. 2013

Chemistry A European J

View full text Add to dashboard Cite

For the first time, the adaptability of the C=C double bond as a versatile precursor for the postsynthetic modification (PSM) of microporous materials was extensively investigated and evaluated. Therefore, an olefin-tagged 4,4'-bipyridine linker was synthesized and successfully introduced as pillar linker within a 9,10-triptycenedicarboxylate (TDC) zinc paddle-wheel metal-organic framework (MOF) through microwave-assisted synthesis. Different reactions, predominately used in organic chemistry, were tested, leading to the development of new postsynthetic reactions for the functionalization of solid materials. The postsynthetic oxidation of the olefin side groups applying osmium tetroxide (OsO₄) as a catalyst led to the formation of a microporous material with free vicinal diol functionalities. The epoxidation with dimethyldioxirane (DMDO) enabled the synthesis of epoxy-functionalized MOFs. In addition to that, reaction procedures for a postsynthetic hydroboration with borane dimethyl sulfide as well as a photoinduced thiol-ene click reaction with ethyl mercaptan were developed. For all of these PSMs, yields of more than 90% were obtained, entirely maintaining the crystallinity of the MOFs. Since the direct introduction of the corresponding groups by means of pre-synthetic approaches is hardly possible, these new PSMs are useful tools for the functionalization of porous solids towards applications such as selective adsorption, separation, and catalysis.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Functionalization of Metal–Organic Frameworks through the Postsynthetic Transformation of Olefin Side Groups

Hindelang

Kronast

Vagin

et al. 2013

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The double bond provides a convenient prospective site for functionality modulation on the molecule . In our early work, we exploited it for the introduction of hydroxyl groups for the preparation of the sugar fragment .…”

Section: Reactivity Profile Of Vince Lactammentioning

confidence: 99%

“…The double bond provides a convenient prospective site for functionality modulation on the molecule. 201 In our early work, we exploited it for the introduction of hydroxyl groups for the preparation of the sugar fragment. 202 The facial selectivity introduced at the stage of hydroxylation has considerable implications on the stereogenic properties of the later products.…”

Section: Hydroxylation Of Vince Lactammentioning

confidence: 99%

2-Azabicyclo[2.2.1]hept-5-en-3-one: Chemical Profile of a Versatile Synthetic Building Block and its Impact on the Development of Therapeutics

2012

View full text Add to dashboard Cite

| Chem. Rev. 2012, 112, 4642−4686 4.4.3. Enantioselective Synthesis of Various Heterocyclic Compounds via ROM-RCM Domino Metathesis of Ring-Opened Vince Lactam Derivatives 4669 4.5. Use of Vince Lactam as a Standard in Chemical Analysis of Compounds and Optical Activity of Stereoisomers 4669 5. Conclusions 4669 Author Information 4669 Corresponding Author 4669 Notes 4669 Biographies 4670 Acknowledgments 4670 Abbreviations 4670 References 4671V). The well-known preference of the hydrolase enzymes to attack a substrate from si face rather than re face was studied in the system via molecular modeling of the two tetrahedral intermediates. These studies revealed that the complexes modeled on re face for both the isomers of the racemate were highly unfavorable. Furthermore, the unpropitious steric Scheme 12. Biocatalytic Resolution of Vince Lactam Followed by Various Chemical Transformations to Obtain the Desired Stereoisomers of Synthetic Intermediates Scheme 13. Proposed Mechanistic Pathway for the Biocatalytic Hydrolysis of Vince Lactam Chemical Reviews Review dx.

show abstract

“…Thus, metal‐ [ 6 ] and organocatalyzed [ 7 ] epoxidations have been reported. Similarly, dihydroxylations can also be achieved via metal‐catalyzed oxidations with H 2 O 2 , (hypo‐)chlorite, or oxygen [ 8 ] as the terminal oxidants. Oxidative cleavage of olefins, traditionally carried out by ozonolysis, can be performed by palladium‐catalyzed aerobic oxidation, [ 9 ] among other methods.…”

Section: Introductionmentioning

confidence: 99%

One‐pot multistep electrochemical strategy for the modular synthesis of epoxides, glycols, and aldehydes from alkenes

Jud

Kappe

Cantillo

2021

Electrochemical Science Adv

View full text Add to dashboard Cite

Oxidative functionalization of alkenes is a versatile strategy for the preparation of many oxygen‐containing scaffolds, such as epoxides, diols, or carbonyl‐containing compounds. In addition to conventional chemical methods, which rely on the utilization of stoichiometric amounts of oxidizing reagents, some electrochemical procedures have been developed to achieve these transformations. Typical electrochemical procedures employ tailored and often complex redox mediators to achieve the target transformation. Herein we present a modular approach for the synthesis of epoxides, diols, and aldehydes from a single set of reaction components. With sodium bromide as an inexpensive electrocatalyst and water as the oxygen donor, the outcome of the reaction (epoxide, 1,2‐diol, or aldehyde) can be selected by simply tuning the electrolysis conditions. This convenient platform has been accomplished by developing a selective one‐pot three‐step bromide‐electrocatalyzed epoxidation/ring opening/carbon‐carbon cleavage sequence. Its modularity permits the selection of the desired product, as the sequential reaction can be ended when the target compound has been formed. The method has been applied to a diversely functionalized terminal and non‐terminal olefins.

show abstract

Recent Developments in Metal‐Catalyzed Dihydroxylation of Alkenes

Cited by 10 publications

References 159 publications

Functionalization of Metal–Organic Frameworks through the Postsynthetic Transformation of Olefin Side Groups

Functionalization of Metal–Organic Frameworks through the Postsynthetic Transformation of Olefin Side Groups

2-Azabicyclo[2.2.1]hept-5-en-3-one: Chemical Profile of a Versatile Synthetic Building Block and its Impact on the Development of Therapeutics

One‐pot multistep electrochemical strategy for the modular synthesis of epoxides, glycols, and aldehydes from alkenes

Contact Info

Product

Resources

About