The Resolution of Important Pharmaceutical Building Blocks by Palladium‐Catalyzed Aerobic Oxidation of Secondary Alcohols

Caspi, Daniel D.; Ebner, D. C.; Bagdanoff, Jeffrey T.; Stoltz, Brian M.

doi:10.1002/adsc.200303188

Cited by 55 publications

(29 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Other functional groups on the alcohol substrate, including protected amines (entries 9 and 10), a tertiary alcohol (entry 11), and even aryl bromides (entries 11 and 12), are tolerated under the reaction conditions. [44]…”

Section: Resultsmentioning

confidence: 99%

“…[51] A number of alcohols successfully resolved are intermediates in the synthesis of a variety of pharmaceuticals (Scheme 8). [44, 52] Boc-protected γ-aminoalcohol (−)- 32 , resolved with good selectivity, is an intermediate in the synthesis of a number of related antidepressants, including fluoxetine·HCl ( 33 ). Tertiary alcohol (−)- 34 and a related ester were transformed to a known intermediate in the synthesis of the leukotriene receptor antagonist montelukast sodium ( 35 ).…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

The Palladium‐Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

Ebner

Bagdanoff

Ferreira

et al. 2009

Chemistry A European J

View full text Add to dashboard Cite

The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (−)-sparteine as chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of base and hydrogen bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 °C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good to excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

The Palladium‐Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

Ebner

Bagdanoff

Ferreira

et al. 2009

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…At this stage, optically pure material could be optained by the oxidative kinetic resolution protocol previously developed in our laboratory. [23] Advancement to diazoacetoacetate 30 was achieved through another three step sequence. [24] The key donor–acceptor cyclopropane 34 was obtained in moderate yield upon heating 30 with Cu(TBS) 2 in toluene or DCE.…”

Section: Use Of Donor–acceptor Cyclopropanes As Intermediates In Natumentioning

confidence: 99%

Synthetic Applications and Methodological Developments of Donor−Acceptor Cyclopropanes and Related Compounds

O’Connor

Wood

Stoltz

2016

Israel Journal of Chemistry

View full text Add to dashboard Cite

Donor–acceptor cyclopropanes are convenient precursors to reactive and versatile 1,3-dipoles, and have found application in the synthesis of a variety of carbo- and heterocyclic scaffolds. This perspective review details our laboratory’s use of donor–acceptor cyclopropanes as intermediates toward the total synthesis of various natural products. We also discuss our work in the development of novel cycloadditions and rearrangements of donor–acceptor cyclopropanes and aziridines, as well as an example of an aryne insertion proceeding via fragmentation of a transient donor–acceptor cyclobutane.

show abstract

“…( S , S ) -2 makes a matched pair with ( − ) -sparteine and exhibits higher selectivity than ( R , R ) -2 . substances including Prozac ® , Singulair ® , and Merck ' s h -NK1 receptor antagonist reported by Stoltz and coworkers (Scheme 11.8 ) [16] . The total synthesis of (+) -amurensinine, a member of the isopavine family that exhibits important biological activities toward Alzheimer ' s and Parkinson ' s diseases, was also accomplished by using the palladium catalysis (Scheme 11.9 ) [17] .…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Oxidations and Related Reactions

Matsumoto

Katsuki

2010

Catalytic Asymmetric Synthesis

View full text Add to dashboard Cite

GENERAL INTRODUCTIONOxidation is a fundamental technology for converting bulk chemicals into valuable materials and is also a useful tool for sophisticated functionalization of organic molecules. Thus, intensive research efforts have been devoted to the development of selective and practical oxidation methods, and a wide variety of chiral metal -based catalysts and organocatalysts have been developed for catalytic asymmetric oxidation reactions in industry and academia in the last half -century [1] . In contrast to the rapid improvement in stereoselectivity, the enhancement of atom economy [2] falls behind. While atom effi ciency (especially active oxygen content in oxygenation reactions) of stoichiometric oxidants is a factor that should be considered, most of the catalytic asymmetric oxidations still use conventional stoichiometric oxidants of low atomeffi ciency such as peracids, alkyl hydroperoxides, hypervalent iodine reagents, hypochlorite, and N -oxide compounds (Table 11.1 ). The use of such oxidants causes the formation of large amounts of undesirable waste. From the viewpoint of ecological sustainability, oxidation with a higher atom -effi cient, safe, abundant, and preferably inexpensive oxidant is favorable. Considering the requirements, molecular oxygen and hydrogen peroxide are the oxidants of choice [3] . Molecular oxygen offers a large advantage because it is abundant in air and is inexpensive. Aerobic oxidation that directly uses ambient air as an oxidant is similar to respiration in living organisms. Hydrogen peroxide is also recognized as a green oxidant. It is almost as equally atomeffi cient as molecular oxygen, and the by -product is safe and clean water. Moreover, its aqueous solution (typically 30 -35%) is inexpensive and easy to handle. Consequently, the development of catalytic asymmetric oxidations with molecular oxygen Catalytic Asymmetric Synthesis, Third Edition, Edited by Iwao Ojima

show abstract

The Resolution of Important Pharmaceutical Building Blocks by Palladium‐Catalyzed Aerobic Oxidation of Secondary Alcohols

Cited by 55 publications

References 16 publications

The Palladium‐Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

The Palladium‐Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

Synthetic Applications and Methodological Developments of Donor−Acceptor Cyclopropanes and Related Compounds

Asymmetric Oxidations and Related Reactions

Contact Info

Product

Resources

About