The Photo-Dehydro-Diels-Alder Reaction: An Efficient Route to Naphthalenes

Wessig, Pablo; Müller, Gunnar; Kühn, Andrea A.; Herre, Robert; Blumenthal, Haiko; Troelenberg, Stefanie

doi:10.1055/s-2005-865316

Cited by 32 publications

(18 citation statements)

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“…In contrast to our previous observation [5], we found that the Me group in the attacked position does not undergo a 1,2-migration, but is obviously trapped by the solvent (XH) from cycloallenes CA(1) and CA(3), respectively (Scheme 5). Although the naphthalenes 12m (from 1m) and 11n (from 1n) were formed as main products, we also isolated compounds 16 and 17, originating from an attack of the mesityl group.…”

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Synthesis of Benzo[g]isochromenes through Photo-Dehydro-Diels–Alder Reaction

Wessig

Müller

Herre

et al. 2006

HCA

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The Photo‐Dehydro‐Diels–Alder (PDDA) reaction is shown to be a versatile method for the preparation of highly functionalized naphthalenes. Thus, ketones 1 could be cyclized to the 1H‐benzo[g]isochromen‐4‐(3H)‐ones 11 and 12, mostly in good yields. The influence of various substituents on the regioselectivity of the reaction was investigated, and the mechanism is discussed based on theoretical calculations.

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“…treatment with lithium phenylacetylide (LPA). MeO(Me)NH · HCl, (i-Pr) 2 described [5], we assume that the photochemical ring-closure proceeds via the biradicals BR(1) as intermediates (Scheme 4). Finally, the target ketones 1o -r were obtained in two steps via the corresponding Weinreb amides (WA).…”

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Synthesis of Benzo[g]isochromenes through Photo-Dehydro-Diels–Alder Reaction

Wessig

Müller

Herre

et al. 2006

HCA

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“…The Photo-Dehydro-Diels-Alder (PDDA) reaction has been proven as versatile method for the preparation of highly functionalized aryl-naphthalenes and binaphthyles [1][2][3][4][5][6]. In continuation of this work, we investigated the capability of the PDDA reaction for macrocyclizations.…”

Section: Discussionmentioning

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Crystal structure of 3,4-diacetyl-15,21-dioxatetracyclo-[23.4.0.02,7.06,11]nonacosa-1(29),2,4,6,8,10,25,27-octaene-14,22-dione — water (1:2), C31H32O6 · 2H2O

Wessig¹,

Matthes²,

Schilde³

2010

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialThe title compound was synthesized via Photo-Dehydro-DielsAlder (PDDA) reaction by irradition of the pentane-1,5-diyl-(3-[2-{3-oxobut-1-ynyl}phenyl)propanoate for 50 min in t-butanol (yield 29 %).The product (37 mg, 0.076 mmol) was solved in 2mlofamixture of diethylether/isopentane/ethanol (5:5:2) after isolation by column chromatography (hexane/ethyl acetate 3:2) and removing the solvent. Colourless needle-like crystals were formed by slowly vaporizing the solvent. Experimental detailsThe O3···C28 moiety is disordered over two sides with an occupation ratio of 0.5/0.5. The hydrogen atoms on the aromatic rings were located from the difference Fourier map. The other hydrogen atoms were calculated in their expected positions. All H atoms were included in the refinement as riding atoms with U iso (H) =1 .2 U eq (C). The crystal structure contains disordered water as solvate molecules. In spite of several attempts, the electronic density in this area could not be resolved satisfactorily. Therefore the contribution of the disordered solvent species was subtracted from the structure factor calculations by the SQUEEZE instruction of the program PLATON. Using that program atotal potential solvent area of 342 Å (11.8 %ofthe unit cell) and an electron count of 68 were calculated, which corresponds with about two water molecules per asymmetric unit. DiscussionThe Photo-Dehydro-Diels-Alder (PDDA) reaction has been proven as versatile method for the preparation of highly functionalized aryl-naphthalenes and binaphthyles [1][2][3][4][5][6]. In continuation of this work, we investigated the capability of the PDDA reaction for macrocyclizations. The 21-membered macrocyclic ring contains a1,5-bridged naphthalene moiety and the compound may therefore be regarded as a cyclophane [7]. Furthermore, the free rotation around the single bond connecting the naphthalene ring and the phenyl ring is disabled due to steric hindrance and, consequently, this bond is a chirality axis. The absolute configuration of the drawn molecule is R with respect to this axis. Because of the centrosymmetric space group the other enantiomer also exists in the crystal. In spite of the 1,5-bridge the naphthalene ring is only weakly distorted from planarity, which can be seen from the torsion angle C1-C9-C10-C5 being 2.8(2)°.B yc ontrast, in [2](1,5)-naphthalino[2]-(2,6)pyridinophan and 1 2,13,14,18-tetracyano-5(1,4)-benzena-1(1,5)-naphthalenacyclooctaphane the chiralic deformations of the naphthalene plane are 28.1° [8] and 11.7° [9]. As in these compounds the bond lengths of the central moiety of the naphthalene ring (C2-C9, C9-C10, C6-C10, C5-C10, C1-C9) are longer (1.416 -1 .427 Å)t han the peripheric ones (1.360 -1 .397 Å), with the exception of C3-C4 (1.431 Å), whose carbon atoms are acetylated. The phenyl ring is nearly perpendicular to the naphthalene ring. The corresponding torsion angle C10-C5-C15-C16 was found to be 96.6(3)°.

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“…This synthetic approach differs from most other routes to naphthalenophanes in that the naphthalene moiety is not present in the reactants but is formed in the cyclization step by means of the Photo-Dehydro-Diels-Alder (PDDA) reaction [6,7], which is a special case of the Dehydro-Diels-Alder (DDA) reaction [8]. In recent years we have intensively investigated the PDDA reaction and established it as a powerful method for the preparation of biaryls [9,10,11,12,13]. Herein we report in continuation of the above mentioned work on the synthesis of 1,6- and 1,8-naphthalenophanes (Figure 1).…”

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Photochemical Synthesis and Properties of 1,6- and 1,8-Naphthalenophanes

Wessig

Matthes

2013

Molecules

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Various 1,6- and 1,8-naphthalenophanes were synthesized by using the Photo-Dehydro-Diels-Alder (PDDA) reaction of bis-ynones. These compounds are easily accessible from ω-(3-iodophenyl)carboxylic acids in three steps. The obtained naphthalenophanes are axially chiral and the activation barrier for the atropisomerization could be determined in some cases by means of dynamic NMR (DNMR) and/or dynamic HPLC (DHPLC) experiments.

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The Photo-Dehydro-Diels-Alder Reaction: An Efficient Route to Naphthalenes

Cited by 32 publications

References 6 publications

Synthesis of Benzo[g]isochromenes through Photo-Dehydro-Diels–Alder Reaction

Synthesis of Benzo[g]isochromenes through Photo-Dehydro-Diels–Alder Reaction

Crystal structure of 3,4-diacetyl-15,21-dioxatetracyclo-[23.4.0.02,7.06,11]nonacosa-1(29),2,4,6,8,10,25,27-octaene-14,22-dione — water (1:2), C31H32O6 · 2H2O

Photochemical Synthesis and Properties of 1,6- and 1,8-Naphthalenophanes

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