Synthesis of homoallylic alcohols

Crandall, Jack K.; Banks, D. B.; Colyer, R. A.; Watkins, Richard J.; Arrington, J. P.

doi:10.1021/jo01265a089

Cited by 123 publications

(45 citation statements)

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“…3,4-Epoxycyclohexene and 3-cyclohexenol were synthesized as described by Crandell et al (64). 3-Cyclohexen-1-one was synthesized by modification of the procedure described Dzingeleski et al (49) and is described in the following paragraph.…”

Section: Methodsmentioning

confidence: 99%

Determining the catalytic role of remote substrate binding interactions in ketosteroid isomerase

Schwans

Kraut

Herschlag

2009

Proc. Natl. Acad. Sci. U.S.A.

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O ver the past decades, visualization of enzyme threedimensional structures has revealed that active sites are located in crevices or pockets. Within these active sites are found coenzymes, cofactors, metal ions, and side chains that participate in a rich array of chemical reactions. Based on this information and decades of enzymology and bioorganic chemistry, reasonable chemical mechanisms using these groups can be posited for most enzymatic reactions. Nevertheless, we still cannot quantitatively account for the enormous enzymatic rate enhancements and exquisite specificities observed by enzymes.Over the past century, Polanyi, Haldane, Pauling, and Jencks recognized a key distinguishing feature between chemical reactions taking place in an enzyme's active site and the corresponding reaction taking place in solution (1-4). Even if the enzymatic and solution reactions use the same cofactors, metal ions, and functional groups, an enzyme can use noncovalent interactions between the enzyme and substrate to accelerate the reaction. Indeed, binding interactions between enzymes and substrates, both directly at the site of chemical transformation and with nonreacting portions of the substrate have been shown to contribute to catalysis (e.g., refs. 5-19). The mechanisms by which these noncovalent interactions can assist catalysis have been widely discussed, as briefly described in the following two paragraphs.In the simplest scenario an enzyme can use binding interactions to localize the substrate to the active site. Beyond simple localization, these binding interactions can correctly position the reactive portion of a substrate relative to active site functional groups and relative to other substrates (7, 20-25). Concomitant with substrate binding solvent is displaced and excluded from the active site and solvent exclusion may be important in shaping the electrostatic environment within the active site (26,27). Indeed, solvent exclusion by substrate binding has been suggested to be important for catalysis in numerous enzymes (e.g., refs. 26-32).Jencks and others realized that remote binding interactions can do more than provide for tight binding between substrate and enzyme. Reactions of bound substrates can be facilitated by use of so-called ''intrinsic binding energy'', which can pay for substrate desolvation, distortion, electrostatic destabilization, and entropy loss (3,7,33,34). The term intrinsic binding energy is not a molecular explanation for catalysis, but rather provides a conceptual framework for analyzing the energetics of enzymatic catalysis. In this scenario the maximum binding energy is not realized in the ground state, because aspects of the bound state, such as restricted positioning of substrates, are energetically unfavorable relative to the interactions and freedom of motion in aqueous solution. However, changes associated with achievement of the transition state, such as charge and geometric rearrangements and the formation of partial covalent bonds between positioned substrates, allow the binding ...

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Section: Methodsmentioning

confidence: 99%

Determining the catalytic role of remote substrate binding interactions in ketosteroid isomerase

Schwans

Kraut

Herschlag

2009

Proc. Natl. Acad. Sci. U.S.A.

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“…They were prepared according to the procedure of Crandall et al, [34] except for the oxiranes 21 and 25, which were prepared according to the two-step procedure described by Matteson et al [32] and Lautens et al [35] General Procedure for the Nucleophilic Opening of Epoxides with Lithium Tributylzincate: In a 25-mL, two-necked flask equipped with a thermometer was placed 3 mL (3 mmol) of a 1  solution of ZnBu 2 in hexane in the required solvent (7 mL) under nitrogen. The solution was cooled to Ϫ20°C and 1.6 mL (3 mmol) of a 1.9 …”

Section: Preparation Of the Epoxidesmentioning

confidence: 99%

Regioselective S_N2 Opening of Vinylic Epoxides with Trialkylzincates and Trialkylaluminates

2004

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The use of trialkylorganozincates and tetraalkylaluminates allows regioselective SN2 nucleophilic opening of vinylic epoxides. The reaction occurs with an anti‐substitution pattern and can be applied to a wide range of substrates. We also show that the solvent and the structure of the epoxide have an influence on the substitution products’ ratio. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…2). The key intermediate for the preparation of all of these compounds is 3-cyclopentenol, which is readily prepared from cyclopentadiene [7,17,18]. Epoxidation of 3-cyclopentenol with mCPBA led to a bicyclic alcohol with cis orientation of the epoxide ring relative to the hydroxyl function with only a trace of the trans isomer, while the benzyl ether of 3-cyclopentenol gave the cis and trans isomers in a 1:1 ratio.…”

Section: Resultsmentioning

confidence: 99%

1,2,4‐Trisubstituted Cyclopentanes as Platforms for Diversity

Guan

Bissantz

Bergstrom

et al. 2012

Archiv der Pharmazie

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Despite their simplicity, relatively few examples of 1,2,4 (1,3,4)-amino-, azido-, and hydroxysubstituted cyclopentanes are reported in the literature. We found that cyclopent-3-en-1-ol can be transformed into a significant variety of compounds of this class by relatively common and efficient synthetic procedures. Stereochemical control of epoxidation of the cyclopentene double bond can be achieved by varying the substitutents at C4. The C4 substituent and epoxide functional group can be converted into a variety of intermediates with differential protection designed for use in applications requiring regiospecific control for further elaboration of the cyclopentane scaffold.

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Synthesis of homoallylic alcohols

Cited by 123 publications

References 1 publication

Determining the catalytic role of remote substrate binding interactions in ketosteroid isomerase

Determining the catalytic role of remote substrate binding interactions in ketosteroid isomerase

Regioselective S_N2 Opening of Vinylic Epoxides with Trialkylzincates and Trialkylaluminates

1,2,4‐Trisubstituted Cyclopentanes as Platforms for Diversity

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Synthesis of homoallylic alcohols

Cited by 123 publications

References 1 publication

Determining the catalytic role of remote substrate binding interactions in ketosteroid isomerase

Determining the catalytic role of remote substrate binding interactions in ketosteroid isomerase

Regioselective SN2 Opening of Vinylic Epoxides with Trialkylzincates and Trialkylaluminates

1,2,4‐Trisubstituted Cyclopentanes as Platforms for Diversity

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Regioselective S_N2 Opening of Vinylic Epoxides with Trialkylzincates and Trialkylaluminates