Scalable preparation and property investigation of a cis-cyclobutane-1,2-dicarboxylic acid from β-trans-cinnamic acid

Amjaour, Houssein; Wang, Zhihan; Mabin, Micah; Puttkammer, Jenna; Busch, Sullivan; Chu, Qianli

doi:10.1039/c8cc08017h

Cited by 28 publications

(52 citation statements)

References 41 publications

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“…Unfortunately, it turned out that due to the low solubility of these derivatives in water, the concentrations required for a bimolecular reaction could not be accomplished. However, it is well known that [2 + 2] photodimerizations can also be performed in the solid state or with a thoroughly stirred suspension [37,43,78]. Therefore, suspensions of 3b und 3c in water were irradiated with an LED lamp at 450-470 nm to give the 2,2'-(2,4-diphenyl-1,3-cyclobutanediyl)bisquinolizinium 4b and 4c as photoproducts in quantitative yield.…”

Section: Photocycloaddition Reactionsmentioning

confidence: 99%

Reversible photoswitching of the DNA-binding properties of styrylquinolizinium derivatives through photochromic [2 + 2] cycloaddition and cycloreversion

Kölsch¹,

Ihmels²,

Mattay³

et al. 2020

Beilstein J. Org. Chem.

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It was demonstrated that styrylquinolizinium derivatives may be applied as photoswitchable DNA ligands. At lower ligand:DNA ratios (≤1.5), these compounds bind to duplex DNA by intercalation, with binding constants ranging from K b = 4.1 × 104 M to 2.6 × 105 M (four examples), as shown by photometric and fluorimetric titrations as well as by CD and LD spectroscopic analyses. Upon irradiation at 450 nm, the methoxy-substituted styrylquinolizinium derivatives form the corresponding syn head-to-tail cyclobutanes in a selective [2 + 2] photocycloaddition, as revealed by X-ray diffraction analysis of the reaction products. These photodimers bind to DNA only weakly by outside-edge association, but they release the intercalating monomers upon irradiation at 315 nm in the presence of DNA. As a result, it is possible to switch between these two ligands and likewise between two different binding modes by irradiation with different excitation wavelengths.

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Section: Photocycloaddition Reactionsmentioning

confidence: 99%

Reversible photoswitching of the DNA-binding properties of styrylquinolizinium derivatives through photochromic [2 + 2] cycloaddition and cycloreversion

Kölsch¹,

Ihmels²,

Mattay³

et al. 2020

Beilstein J. Org. Chem.

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“…cyclization. [20][21][22][23][24][25][26][27][28] Recently, a major contribution to this field has been exploited by using catalytic amounts of HVIR [29,30] in HFIP to investigate a stereoselective functionalization of alkenes. [31][32][33] The HFIP has been shown to be a unique solvent due to its significant role of hydrogen bonding [34][35][36] that en- ables the HVIR to act as single-electron oxidants.…”

Section: Introductionmentioning

confidence: 99%

“…[ 14–16 ] In this regard, metal complexes [ 17 ] and organic [ 18,19 ] photoredox catalysis have been applied to promote such a nice cyclization. [ 20–28 ] Recently, a major contribution to this field has been exploited by using catalytic amounts of HVIR [ 29,30 ] in HFIP to investigate a stereoselective functionalization of alkenes. [ 31–33 ] The HFIP has been shown to be a unique solvent due to its significant role of hydrogen bonding [ 34–36 ] that enables the HVIR to act as single‐electron oxidants.…”

Section: Introductionmentioning

confidence: 99%

Hypervalent Iodine‐Mediated Styrene Hetero‐ and Homodimerization Initiation Proceeds with Two‐Electron Reductive Cleavage

Hussein

Al-Yasari

2020

Eur J Org Chem

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A mechanistic insight into the hetero‐ and homodimerizations (HETD and HOMD) of styrenes promoted by hypervalent iodine reagents (HVIRs; DMP and PIDA) and facilitated by hexafluoro2‐propanol (HFIP) to yield all‐trans cyclobutanes is reported using density functional theory (DFT) calculations. The initialization involving direct bimolecular one‐electron transfer is found to be highly unfavored, especially for the PIDA system. At this point, we suggest that the reaction is initiated with an overall two‐electron reductive cleavage of two I–O bond cleavages, affording I(III) (iodinane) and I(I) (iodobenzene) product with DMP and PIDA as oxidant, respectively. The resulting acetate groups are stabilized by the solvent HFIP through strong hydrogen bonding interaction, which promotes the electron transfer process. The nature of the electron transfer is studied in detail and found that the overall two‐electron transfer occurs within a trimolecular complex organized by π‐stacking interactions and as a stepwise and concerted mechanism for I(III) and I(V) oxidants, respectively. The reaction rate is determined by the initialization step: for I(III), the initiation is thermodynamically endergonic, whereas the endergonicity for I(V) is modest. Upon initialization, the reaction proceeds through a stepwise [2+2] pathway, involving a radical‐cationic π–π stacked transition states, where the HOMD is a dynamically competing pathway to HETD although the latter is relatively faster.

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“…[14][15][16] In this regard, metal complexes 17 and organic [18][19] photoredox catalysis have been applied to promote such a nice cyclization. [20][21][22][23][24][25][26][27][28] Recently, a major contribution to this field has been exploited by using catalytic amounts of HVIR [29][30] in HFIP to investigate a stereoselective functionalization of alkenes. [31][32][33] The HFIP has been shown to be a unique solvent due its significant role of hydrogen bonding [34][35][36] that enables the HVIR to act as single electron oxidants.…”

Section: Introductionmentioning

confidence: 99%

Hypervalent Iodine-Mediated Styrene Hetero- and Homodimerization Initiation Proceeds with Two-Electron Reductive Cleavage

Hussein¹,

Ma²,

Al-Yasari³

2020

Preprint

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<a>A mechanistic insight into </a>the hetero- and homodimerizations (HETD and HOMD) of styrenes promoted by hypervalent iodine reagents (HVIRs; DMP and PIDA) and facilitated by HFIP to yield all trans cyclobutanes is reported using density functional theory (DFT) calculations. The initialization involving direct bimolecular one-electron transfer is found to be highly unfavored, especially for the PIDA system. At this point, we suggest that the reaction is initiated with an overall two-electron reductive cleavage of two I─O bond cleavages, affording I(III) (iodinane) and I(I) (iodobenzene) product with DMP and PIDA as oxidant, respectively. The resulting acetate groups are stabilized by the solvent HFIP through strong hydrogen bonding interaction, which promotes the electron transfer process. The nature of the electron transfer is studied in detail and found that the overall two-electron transfer occurs within tri-molecular complex organized by π-stacking interactions and as a stepwise and concerted mechanism for I(III) and I(V) oxidants, respectively. The reaction rate is determined by the initialization step: for I(III), the initiation is thermodynamically endergonic, whereas the endergonicity for I(V) is modest. Upon initialization, the reaction proceeds through a stepwise [2+2] pathway, involving a radical-cationic π-π stacked intermediate, either hetero- or homodimerized. DFT results supported by quasiclassical molecular dynamics simulations show that HOMD is dynamically competing pathway to HETD although the latter is relatively faster, in accordance with experimental observations.

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Scalable preparation and property investigation of a cis-cyclobutane-1,2-dicarboxylic acid from β-trans-cinnamic acid

Abstract: Scalable synthesis of CBDA-4, a thermocleavable diacid building block, was accomplished by capturing and photodimerizing a metastable crystalline solid of trans-cinnamic acid.

Cited by 28 publications

References 41 publications

Reversible photoswitching of the DNA-binding properties of styrylquinolizinium derivatives through photochromic [2 + 2] cycloaddition and cycloreversion

Reversible photoswitching of the DNA-binding properties of styrylquinolizinium derivatives through photochromic [2 + 2] cycloaddition and cycloreversion

Hypervalent Iodine‐Mediated Styrene Hetero‐ and Homodimerization Initiation Proceeds with Two‐Electron Reductive Cleavage

Hypervalent Iodine-Mediated Styrene Hetero- and Homodimerization Initiation Proceeds with Two-Electron Reductive Cleavage

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