Total synthesis of (+)-jatropholones A and B.  Exploitation of the high-pressure technique

Smith, Amos B.; Liverton, Nigel J.; Hrib, Nicholas J.; Sivaramakrishnan, H.; Winzenberg, Kevin N.

doi:10.1021/ja00271a038

Cited by 63 publications

(20 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…To achieve rate accelerations, an enzyme in aqueous solution must therefore provide more than the hydrophobic effect in solvent alone. A more exotic catalytic device not directly available to enzymes are high pressures of several thousand atmospheres, which have been useful in mechanistic studies and total synthesis . High pressures drive formation of the, relative to the reactants, more compact Diels–Alder transition state …”

Section: How Chemists Accelerate [4+2] Cycloadditionsmentioning

confidence: 99%

“…Am ore exotic catalytic device not directly available to enzymes are high pressures of several thousanda tmospheres,w hich have been usefuli nm echanistic studies and total synthesis. [23,24] High pressuresd rive formation of the, relative to the reactants, more compact Diels-Alder transition state. [25] Enantioselective catalysts often show high stereoselectivity like enzymes but comparep oorly in terms of catalytic efficiency:r eactions typicallyt ake days to reachc ompletion.…”

Section: How Chemists Accelerate [4+ +2] Cycloadditionsmentioning

confidence: 99%

See 1 more Smart Citation

Biocatalytic Strategies towards [4+2] Cycloadditions

Lichman

O’Connor

Kries

2019

Chemistry A European J

View full text Add to dashboard Cite

Long sought after [4+2] cyclases have sprouted up in numerous biosynthetic pathways in recent years, raising hopes for biocatalytic solutions to cycloaddition catalysis, an important problem in chemical synthesis. In a few cases, detailed pictures of the inner workings of these catalysts have emerged, but intense efforts to gain deeper understanding are underway by means of crystallography and computational modelling. This Minireview aims to shed light on the catalytic strategies that this highly diverse family of enzymes employs to accelerate and direct the course of [4+2] cycloadditions with reference to small‐molecule catalysts and designer enzymes. These catalytic strategies include oxidative or reductive triggers and lid‐like movements of enzyme domains. A precise understanding of natural cycloaddition catalysts will be instrumental for customizing them for various synthetic applications.

show abstract

Section: How Chemists Accelerate [4+2] Cycloadditionsmentioning

confidence: 99%

Section: How Chemists Accelerate [4+ +2] Cycloadditionsmentioning

confidence: 99%

Biocatalytic Strategies towards [4+2] Cycloadditions

Lichman

O’Connor

Kries

2019

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…In 1986, Smith and co-workers disclosed the first total synthesis of the diterpenes (+)-jatropholone A (26) and B (27) by employing a high-pressure-induced Diels-Alder reaction to fuse the six-membered ring of the core jatropholone skeleton (Scheme 3). 15 Starting from pyrrolidine enamine 17, hydroxy diketone 19 was prepared in two steps. Acid-catalyzed cyclodehydration of 19 led to an intermediate furanone which was O-methylated to provide furan 20.…”

Section: Scheme 1 Synthesis Of Cantharidin (4) By Daubenmentioning

confidence: 99%

High-Pressure Transformations in Natural Product Synthesis

Hugelshofer

Magauer

2014

Synthesis

View full text Add to dashboard Cite

This review summarizes the application of high-pressure chemistry in natural product synthesis. By highlighting reactions that could not be promoted by conventional means but that proceed readily under high-pressure conditions, we intend to disclose the benefits of high-pressure-mediated reactions for organic transformations. The individual syntheses are classified by the reaction type of the key step and are discussed briefly.

show abstract

“…Diels-Alder reactions using furans as diene partners represent a powerful methodology for the construction of variously polyoxygenated 6-membered rings [1][2][3][4][5][6][7][8]. Thus, cycloaddition under high pressure of 2-(/m-butyldimethylsilyloxy)-5-methylfurane to 4-methoxycyclopentenone afforded a mixture of two diastereoisomers.…”

Section: Source Of Materialsmentioning

confidence: 99%

Crystal structure of (3R,3aR,4S,7S,7aR*)-4-(tert-butyldimethylsilyloxy)-4,7-epoxy-3-methoxy-7-methyloctahydro-1H-inden-1-one, C17H30O4Si

Tinant

Trembleau

Ghosez

2000

Zeitschrift Für Kristallographie - New Crystal Structures

View full text Add to dashboard Cite

Total synthesis of (+)-jatropholones A and B. Exploitation of the high-pressure technique

Cited by 63 publications

References 7 publications

Biocatalytic Strategies towards [4+2] Cycloadditions

Biocatalytic Strategies towards [4+2] Cycloadditions

High-Pressure Transformations in Natural Product Synthesis

Crystal structure of (3R,3aR,4S,7S,7aR*)-4-(tert-butyldimethylsilyloxy)-4,7-epoxy-3-methoxy-7-methyloctahydro-1H-inden-1-one, C17H30O4Si

Contact Info

Product

Resources

About

Total synthesis of (+)-jatropholones A and B. Exploitation of the high-pressure technique

Cited by 63 publications

References 7 publications

Biocatalytic Strategies towards [4+2] Cycloadditions

Biocatalytic Strategies towards [4+2] Cycloadditions

High-Pressure Transformations in Natural Product Synthesis

Crystal structure of (3R*,3aR*,4S*,7S*,7aR*)-4-(tert-butyldimethylsilyloxy)-4,7-epoxy-3-methoxy-7-methyloctahydro-1H-inden-1-one, C17H30O4Si

Contact Info

Product

Resources

About

Crystal structure of (3R,3aR,4S,7S,7aR*)-4-(tert-butyldimethylsilyloxy)-4,7-epoxy-3-methoxy-7-methyloctahydro-1H-inden-1-one, C17H30O4Si