Ring strain-dictated divergent fluorinating Prins cyclization or semipinacol rearrangement

Liu, Yi; Yeung, Ying‐Yeung

doi:10.1039/c7ob01567d

Cited by 12 publications

(6 citation statements)

References 41 publications

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“…Two X‐ray structures of molecules containing a shielded tertiary and secondary alkyl fluorine atom involved in intermolecular HBs along with the geometry of these HBs are shown in Figure 8 [48,49] …”

Section: Resultsmentioning

confidence: 99%

“… X‐ray structure of a tertiary (top) and secondary (bottom) alkyl fluoride involved in an intermolecular HB. The structures are KEFMIU [48] (top) and BACMIE [49] (bottom). The HB are displayed with dotted lines and the geometry of the HB is reported close to the respective structure.…”

Section: Resultsmentioning

confidence: 99%

“…lecular HBs along with the geometry of these HBs are shown in Figure 8. [48,49] It is worth noting the very short F•••H distances for the formed HBs in the two structures. In the molecule KEFMIU (Figure 8 top) a HB with a water molecule trapped during the crystallization process is observed, providing crystallographic evidence that a shielded fluorine atom can make a HB complex with water.…”

Section: Small-molecule X-ray Structures Showing Hb Involving Fluorin...mentioning

confidence: 95%

“…[5,9,53,54] The ab initio quantum-mechanical computed computed geometrical values of the HB complexes with alkyl fluorine atom as HBA between CH 3 OH and fluorocyclohexane, [21] between CH 3 OH and CH 3 CH 2 F, [17] between H 2 O and CH 3 F [7] and between H 2 O and CH 3 CH 2 F, [20] displayed with open circles in Figure 9, compare favorably with the experimental results derived from the CSD analysis. [48] (top) and BACMIE [49] (bottom). The HB are displayed with dotted lines and the geometry of the HB is reported close to the respective structure.…”

Section: Small-molecule X-ray Structures Showing Hb Involving Fluorin...mentioning

confidence: 99%

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Hydrogen Bond Acceptor Propensity of Different Fluorine Atom Types: An Analysis of Experimentally and Computationally Derived Parameters

Vulpetti

Dalvit²

2021

Chemistry A European J

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The propensity of organic fluorine acting as a weak hydrogen bond acceptor (HBA) in intermolecular and intramolecular interactions has been the subject of many experimental and theoretical studies often reaching different conclusions. Over the last few years, new and stronger evidences have emerged for the direct involvement of fluorine in weak hydrogen bond (HB) formation. However, not all the fluorine atom types can act as weak HBA. In this work, the differential HBA propensity of various types of fluorine atoms was analyzed with a particular emphasis for the different types of alkyl fluorides. This was carried out by evaluating ab initio computed parameters, experimental 19F NMR chemical shifts and small molecule crystallographic structures (extracted from the CSD database). According to this analysis, shielded (with reference to the 19F NMR chemical shift) alkyl mono‐fluorinated motifs display the highest HBA propensity in agreement with solution studies. Although much weaker than other well‐characterized HB complexes, the fragile HBs formed by these fluorinated motifs have important implications for the chemical‐physical and structural properties of the molecules, chemical reactions, and protein–ligand recognition.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Small-molecule X-ray Structures Showing Hb Involving Fluorin...mentioning

confidence: 95%

Section: Small-molecule X-ray Structures Showing Hb Involving Fluorin...mentioning

confidence: 99%

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Hydrogen Bond Acceptor Propensity of Different Fluorine Atom Types: An Analysis of Experimentally and Computationally Derived Parameters

Vulpetti

Dalvit²

2021

Chemistry A European J

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“…A single fluorine atom was contained in the cyclized products. If we succeed in combining other halogenation reactions, such as chlorination and bromination, with the bicyclization, it would greatly increase the value of our reaction because the halogen group introduced is useful for subsequent derivatization processes [24][25][26][27][28][29][30][31][32]. In this work, we have studied the possibility of the introduction of Cl and Br atoms in the termination of the integrated Prins cyclization using (E)-octa-3,7-dien-1-ol (Scheme 1(b)).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of halogenated bicyclic molecules involving Prins cyclization from aldehydes and non-conjugated diene alcohol

Matsumoto¹,

Ohtsuka²,

Hasebe³

et al. 2021

Preprint

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The reactions of aldehydes and a non-conjugated alcohol, (E)-octa-3,7-dien-1-ol, in the presence of halogen-containing reagents afforded the corresponding halogenated bicyclic molecules in good yields. The optimization, scope and limitations of the reactions as well as scale-up reactions have been examined. Quantum chemical calculations helped clarify the microscopic mechanism of a key reaction process, the introduction of a Cl atom to a bicyclic carbocation.

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Modulating Prins Cyclization versus Tandem Prins Processes for the Synthesis of Hexahydro‐1H‐pyrano[3,4‐c]chromenes

et al. 2020

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We propose the synthesis of biologically relevant hexahydro‐1H‐pyrano[3,4‐c]chromenes, via a tandem Prins/Friedels‐Crafts process, catalyzed by BF3.Et2O, starting from (E)‐ and (Z)‐5‐phenoxypent‐3‐en‐1‐ol. The diastereoselectivity of the process is controlled by the geometry of the homoallylic alcohol. We also point out that the Prins product can be obtained in high yields and good diastereoselectivity when the reaction is promoted by AlCl3 as Lewis acid in the presence of an external nucleophile.

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Ring strain-dictated divergent fluorinating Prins cyclization or semipinacol rearrangement

Abstract: We have developed ring-strain dictated divergent diastereoselective fluorinating Prins cyclization reactions or semipinacol rearrangement reactions to access tetrahydropyrans containing a fluorohydrin or a carbonyl moiety at quaternary carbon centers under mild conditions, respectively.

Cited by 12 publications

References 41 publications

Hydrogen Bond Acceptor Propensity of Different Fluorine Atom Types: An Analysis of Experimentally and Computationally Derived Parameters

Hydrogen Bond Acceptor Propensity of Different Fluorine Atom Types: An Analysis of Experimentally and Computationally Derived Parameters

Synthesis of halogenated bicyclic molecules involving Prins cyclization from aldehydes and non-conjugated diene alcohol

Modulating Prins Cyclization versus Tandem Prins Processes for the Synthesis of Hexahydro‐1H‐pyrano[3,4‐c]chromenes

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