Sequential Diels–Alder Reaction/Rearrangement Sequence: Synthesis of Functionalized Bicyclo[2.2.1]heptane Derivatives and Revision of Their Relative Configuration

Liang, Demin; Zou, Yue; Wang, Quanrui; Goeke, Andreas

doi:10.1021/jo500942a

Cited by 9 publications

(3 citation statements)

References 26 publications

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“…The reaction sequence is believed to proceed with a consecutive Diels–Alder reaction and two 1,2-shift rearrangements. Upon the formation of Diels–Alder product 30 , its angular aldehyde moiety was complexed/catalyzed with LA (i.e., SnCl 4 ) to form the oxonium ion, which in turn underwent an electrophilic addition with the alkene to give carbocation species A-I (like Prins reaction), by which a cascade of 1,2-hydride and 1,2-alkyl carbanion shifts sequentially occurred via species A-II to achieve diketone 29 , as similar to the previous report by Wang and coworkers [ 27 ].…”

Section: Resultssupporting

confidence: 83%

A Convenient Diels-Alder Approach toward Potential Polyketide-like Antibiotics Using α-Activated α,β-Unsaturated 4,4-Dimethyl-1-tetralones as Dienophiles

et al. 2023

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Making use of a Diels–Alder approach based on various α,β-unsaturated 2-carbomethoxy-4,4-dimethyl-1-tetralones as novel dienophiles, the corresponding polycyclic adducts could be efficiently synthesized in good to high yields (74~99%) in the presence of Lewis acid (e.g., SnCl4). Accordingly, a synthetically useful platform is established to provide a focused aromatic polyketide-like library for screening of potential natural and non-natural antimicrobial agents.

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Section: Resultssupporting

confidence: 83%

A Convenient Diels-Alder Approach toward Potential Polyketide-like Antibiotics Using α-Activated α,β-Unsaturated 4,4-Dimethyl-1-tetralones as Dienophiles

et al. 2023

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“…The Diels–Alder reaction usually occurs with outstanding stereochemical control and provides an efficient way of synthesizing six-membered rings. Various functional groups of natural products such as decalin, bicyclo[2.2.2]octane, bicyclo[2.2.1]heptane, spiro-tetramic acid, spiro-tetronic acid, and more complex fused cyclic systems are also biosynthesized by Diels–Alder reactions . Two Diels–Alderases are involved in the biosynthesis of the pyrroindomycin family of natural products such as pyrroindomycin A ( 1 ) and B ( 2 ), which possess significant antimicrobial bioactivities toward MRSA and vancomycin-resistant Enterococci .…”

Section: Introductionmentioning

confidence: 99%

Computational Investigation of the Mechanism of Diels–Alderase PyrI4

et al. 2020

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We studied the mechanisms of activation and stereoselectivity of a monofunctional Diels−Alderase (PyrI4)-catalyzed intramolecular Diels−Alder reaction that leads to formation of the key spirotetramate moiety in the biosynthesis of the pyrroindomycin family of natural products. Key activation effects of PyrI4 include acid catalysis and an induced-fit mechanism that cooperate with the unique "lid" feature of PyrI4 to stabilize the Diels−Alder transition state. PyrI4 enhances the intrinsic Diels−Alder stereoselectivity of the substrate and leads to stereospecific formation of the product.

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“…Cyclic dienes such as 1,2-dimethylenecyclohexane (1) and 1,2-dimethylenecyclopentane (2) have attracted interest because their production of multicyclic adducts which are used as a starting material to synthesize of many natural products by using the Diels Alder reaction and electrophilic addition of their conjugated double bonds ( Figure 1) [1][2][3][4][5][6][7][8][9]. (2) Brominated compounds, which are used as intermediates in the synthesis of many compounds, have synthetic importance as a starting material.…”

Section: Introductionmentioning

confidence: 99%

Bromination of 1,2-Dimethylenecyclohexane: Temperature Effect on Product Distribution

Altundaş¹

2019

Gazi University Journal of Science

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Highlights• The bromination reactions of 1,2-dimethylcyclohexane were examined. • The reaction temperatures and the amount of the bromine affected the product distributions. • As the temperature increased, it caused a decrease in the amount of kinetically controlled product • The rise in temperature led to an increase in radicalic addition products.• Increasing the amount of bromine produced an increase in the amounts of radicalic addition products. Article Info AbstractIn this study the electrophlic addition of bromine to an exocyclic diene, 1,2 dimethylenecyclohexane, was investigated. The bromination of 1,2-dimethylenecyclohexane yielded 1,2-bis(bromomethyl)cylohex-1-en at low temperature. Nevertheless, the bromination of 1,2-dimethylenecyclohexane at room temperature gave 1,4 addition product 1,2-bis(bromomethyl)cylohex-1-en as a main product together with 1-bromo-1-(bromomethyl)-2-methylenecylohexane and 3-bromo-1,2-bis(bromomethyl)cyclohex-1-ene. Similarly, high temperature bromination of 1,2-bismethylenecyclohexane gave the radical bromination products (3-bromo-1,2-bis(bromomethyl)cyclohex-1-ene and 3,6-dibromo-1,2bis(bromomethyl)cyclohex-1-ene) in addition to the 1,4 addition product. While the bromination of exocylicdiene at room temperature with excess bromine gave tetrabrominated product 1,2-dibromo-1,2-bis(bromomethyl)cyclohexane as a sole product, the bromination of exocyclicdiene in high temperature with excess bromine resulted in a tetra brominated product 1,2-dibromo-1,2-bis(bromomethyl)cyclohexane and the three brominated product 3-bromo-1,2-bis(bromomethyl)cyclohex-1-ene together with the radicalic tetrabrominated product 3,6-dibromo-1,2-bis(bromomethyl)cyclohex-1-ene as main products. However, the high temperature bromination of 1,4 brominated product with excess bromine provided only the radicalic brominated product 3-bromo-1,2bis(bromomethyl)cyclohex-1-ene and 3,6-dibromo-1,2-bis(bromomethyl)cyclohex-1ene.Thus the functional agents which can be used as starting material in the synthesis of many compounds were synthesized, purified and characterized. Keywords Bromination 1,2DimethylenecyclohexaneHigh temperature bromination Radicalic addition

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Sequential Diels–Alder Reaction/Rearrangement Sequence: Synthesis of Functionalized Bicyclo[2.2.1]heptane Derivatives and Revision of Their Relative Configuration

Cited by 9 publications

References 26 publications

A Convenient Diels-Alder Approach toward Potential Polyketide-like Antibiotics Using α-Activated α,β-Unsaturated 4,4-Dimethyl-1-tetralones as Dienophiles

A Convenient Diels-Alder Approach toward Potential Polyketide-like Antibiotics Using α-Activated α,β-Unsaturated 4,4-Dimethyl-1-tetralones as Dienophiles

Computational Investigation of the Mechanism of Diels–Alderase PyrI4

Bromination of 1,2-Dimethylenecyclohexane: Temperature Effect on Product Distribution

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