High-Pressure Transformations in Natural Product Synthesis

Hugelshofer, Cedric L.; Magauer, Thomas

doi:10.1055/s-0033-1341073

Cited by 30 publications

(3 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…What distinguishes the furan-diene DA reactions from other [4+ +2] cycloadditions is the reactionsr eversibility at near ambient temperatures.I ndeed, the position of the DA equilibrium can generally be shifted in ac ontrolled, predictable,a nd tunable manner,a tt emperatures ideally suited for e.g.,m aterial science applications.F or this reason, the furan DA coupling has been extensively exploited in various macromolecular applications built around reversibility,s uch as responsive materials [4][5][6][7] and drug delivery systems. [8,9] In contrast, other important areas of application require stability rather than reversibility,a sg enerally seen for instance in bioconjugation, [10] natural product synthesis, [11][12][13][14][15] drug dis-covery [16] and the synthesis of renewables-based chemical commodities (Figure 1). [17][18][19][20][21] In such cases,f urther synthetic elaboration of the relatively labile DA adduct is in competition with the kinetically accessible cycloreversion pathway, posing amajor challenge (Figure 2A).…”

Section: Introductionmentioning

confidence: 99%

“…For this reason, the furan DA coupling has been extensively exploited in various macromolecular applications built around reversibility, such as responsive materials [4–7] and drug delivery systems [8, 9] . In contrast, other important areas of application require stability rather than reversibility, as generally seen for instance in bioconjugation, [10] natural product synthesis, [11–15] drug discovery [16] and the synthesis of renewables‐based chemical commodities (Figure 1). [17–21] In such cases, further synthetic elaboration of the relatively labile DA adduct is in competition with the kinetically accessible cycloreversion pathway, posing a major challenge (Figure 2 A).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The Interplay between Kinetics and Thermodynamics in Furan Diels–Alder Chemistry for Sustainable Chemicals Production

et al. 2022

View full text Add to dashboard Cite

Biomass‐derived furanic platform molecules have emerged as promising building blocks for renewable chemicals and functional materials. To this aim, the Diels–Alder (DA) cycloaddition stands out as a versatile strategy to convert these renewable resources in highly atom‐efficient ways. Despite nearly a century worth of examples of furan DA chemistry, clear structure–reactivity–stability relationships are still to be established. Detailed understanding of the intricate interplay between kinetics and thermodynamics in these very particular [4+2] cycloadditions is essential to push further development and truly expand the scope beyond the ubiquitous addend combinations of electron‐rich furans and electron‐deficient olefins. Herein, we provide pertinent examples of DA chemistry, taken from various fields, to highlight trends, establish correlations and answer open questions in the field with the aim to support future efforts in the sustainable chemicals and materials production.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Interplay between Kinetics and Thermodynamics in Furan Diels–Alder Chemistry for Sustainable Chemicals Production

et al. 2022

View full text Add to dashboard Cite

show abstract

“…The effect of pressure on the rate of a chemical reaction is measured by the volume of activation (or activation volume) ∆ ‡ . 5,6,7,8,9,10,11,12,13,14,15,16,17,18 The volume of activation is the volume change of a reaction system from the reactant(s) to the transition state.…”

mentioning

confidence: 99%

High-pressure reaction profiles and activation volumes of 1,3-cyclohexadiene dimerizations computed by the extreme pressure-polarizable continuum model (XP-PCM)

Chen

Houk

Cammi

2021

Preprint

View full text Add to dashboard Cite

Quantum chemical calculations are reported for the thermal dimerizations of 1,3-cyclohexadiene at 1 atm and high pressures up to 6 GPa. Previous experiments [Klärner et al. Angew. Chem. Int. Ed. 1986, 25, 108], based on measured activation energies and activation volumes, suggested concerted mechanisms for the formation of the endo [4+2] cycloadduct and a [6+4]-ene adduct, and stepwise mechanisms for the formation of the exo [4+2] cycloadduct and two [2+2] cycloadducts. Computed activation enthalpies (ωB97XD, CCSD(T) and SC-NEVPT2) of plausible dimerization pathways at 1 atm agree well with the experiment activation energies and the values from previous calculations [Ess et al. J. Org. Chem. 2008, 73, 7586]. High-pressure reaction profiles, computed by the recently-developed extreme pressure-polarizable continuum model (XP-PCM), show that the reduction of reaction barrier is more profound in concerted reactions than in stepwise reactions, which is rationalized on the basis of the volume profiles of different mechanisms. A clear shift of the transition state towards the reactant by high pressure is revealed for the [6+4]-ene reaction by the calculations. The computed activation volumes by XP-PCM agree excellently with the experimental values, confirming the existence of competing mechanisms in the thermal dimerizations of 1,3-cyclohexadiene.

show abstract

Biomimetic Synthesis of (+)‐Aspergillin PZ

et al. 2018

View full text Add to dashboard Cite

The cytochalasans are al arge family of polyketide natural products with potent bioactivities.A mongst them, the aspochalasins show particularly intricate and fascinating structures.T og ain insight into their structural diversity and innate reactivity,w eh ave developed ar apid synthesis of aspochalasin D, the central member of the family.Itproceeded in 13 steps starting from divinyl carbinol and utilized ah igh pressure Diels-Alder reaction that features high regio-and stereoselectivity.Sofar,our work has culminated in abiomimetic synthesis of aspergillin PZ, an intricate pentacyclic aspochalasan.

show abstract

High-Pressure Transformations in Natural Product Synthesis

Cited by 30 publications

References 48 publications

The Interplay between Kinetics and Thermodynamics in Furan Diels–Alder Chemistry for Sustainable Chemicals Production

The Interplay between Kinetics and Thermodynamics in Furan Diels–Alder Chemistry for Sustainable Chemicals Production

High-pressure reaction profiles and activation volumes of 1,3-cyclohexadiene dimerizations computed by the extreme pressure-polarizable continuum model (XP-PCM)

Biomimetic Synthesis of (+)‐Aspergillin PZ

Contact Info

Product

Resources

About