Multibridged [3n]Cyclophanes, 1. Synthesis of [34](1,2,3,5)‐ and ‐(1,2,4,5)Cyclophanes

Shinmyozu, Teruo; Kusumoto, S.; Nomura, Sachiyo; Kawase, Haruo; Inazu, Toshiyuki

doi:10.1002/cber.19931260810

Cited by 22 publications

(22 citation statements)

References 30 publications

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“…The interannular distances of the two faced benzene rings of 3 are 3.03 Å for the shortest (b) and EtOH (85%). [15] Thus, the series of reactions involving chloromethylation, halogen exchange, the TosMIC coupling re-3.20 Å for the longest positions (a), which are similar to corresponding distances in [3.3]paracyclophane (11). [21] action under anhydrous conditions, followed by reductive cleavage of the cyclic TosMIC adduct 7 constitutes a new The distortion angle α of 3 (7.4°) is smaller than that of [2 4 ]cyclophane 9.…”

mentioning

confidence: 74%

“…The non-hydrogen atoms were refined anisotropically, those of an authentic sample. [11] and hydrogen atoms isotopically. All the computations were performed using the teXsan package.…”

Section: Methodsmentioning

confidence: 97%

“…Ϫ FABMS; cal properties were in complete agreement with an authentic sample. [11] The crystals for X-ray crystallography were grown by m/z: 393 [M ϩ ]. Ϫ C 28 H 28 N 2 · 0.5 H 2 O (401.2): calcd.…”

Section: Methodsmentioning

confidence: 99%

“…of 3, was synthesized by a lengthy 12-step procedure from meta-xylene, and the yield of the TosMIC coupling was low. [11] Recently, Vögtle et al reported an improved synthetic method for 5b by the simultaneous introduction of four bromomethyl groups into [3.3]metacyclophane (4) (ca. 50%).…”

mentioning

confidence: 99%

“…Unlike the yield (24%). [11] Since the major reason for this low yield seemed to be the base-catalyzed hydrolysis of the bromo-bridging bonds of [2 4 ](1,2,4,5)cyclophane (9) (1.591 Å ), [19] all the bond lengths and bond angles of 3 are typical values. methyl group of 5b under the reaction conditions, we decided to employ anhydrous conditions; [14] a mixture of 5b The geometry of the benzene ring of 3 is bent from planar to a boat-shaped form.…”

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confidence: 99%

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Improved Synthesis, Structure, and Cycloaddition Reaction of [34](1,2,4,5)Cyclophane

Sentou¹,

Satou²,

Yasutake³

et al. 1999

Eur. J. Org. Chem.

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The modified synthetic route to [34](1,2,4,5)cyclophane (3) provides gram quantities of this compound in fewer steps than the conventional routes. The cycloaddition of 3 with dicyanoacetylene (12) gave barrelenophane 13, which was transformed into semibullvalenophane 15 on photoirradiation. This transformation (13 → 15) is in sharp contrast to the case of Boekelheide's [24]barrelenophane, where cyclooctatetraenophane is obtained. The X‐ray structural analyses of 3, 13, and 15 demonstrates their unique structures.

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mentioning

confidence: 74%

“…The non-hydrogen atoms were refined anisotropically, those of an authentic sample. [11] and hydrogen atoms isotopically. All the computations were performed using the teXsan package.…”

Section: Methodsmentioning

confidence: 97%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Improved Synthesis, Structure, and Cycloaddition Reaction of [34](1,2,4,5)Cyclophane

Sentou¹,

Satou²,

Yasutake³

et al. 1999

Eur. J. Org. Chem.

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Bildung einer neuartigen Käfigverbindung mit einem Pentacyclo[6.3.0.14,11.02,6.05,10]dodecan-Skelett durch Photolyse von [34](1,2,4,5)Cyclophan

Lim

Yasutake

Shinmyozu³

2000

Angewandte Chemie

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Prismane bilden eine faszinierende Familie von (CH) n -Polyedern, [1] aus der einige Mitglieder ± Prisman, [2] Cuban [3] und Pentaprisman [4, 5] ± erfolgreich synthetisiert worden sind. Seit kurzem konzentriert man sich auf das herausfordernde Ziel, höhere Prismane und besonders die Hexaprismane 1 zu synthetisieren. Trotz vieler Versuche haben sich diese der Synthese bisher entzogen, hauptsächlich mangels geeigneter Synthesewege und wegen der gegenüber den niedereren Prismanen zu erwartenden höheren Spannung. Bei unserem Versuch zum Aufbau des Hexaprismanskeletts durch Photolyse mehrfach verbrückter [3 n ]Cyclophane (n 3 ± 6) optimierten wir zunächst die Reaktionsbedingungen unter Verwendung des kleinsten Homologen, [3 3 ](1,3,5)Cyclophan 2.Dabei stellten wir fest, dass 2 bei Bestrahlung mit einer Niederdruck-Hg-Lampe in H 2 O-gesättigtem CH 2 Cl 2 in das Bishomopentaprisman 3 überführt wird. [6] Um die Hexaprisman-Derivate zu synthetisieren und weitere Informationen über den Reaktionsmechanismus zu erhalten, wurde die Photolyse des nächsthöheren Homologen von 2, [3 4 ](1,2,4,5)Cyclophan 4, untersucht, [7] das kürzlich durch eine verbesserte und praktikable Synthesemethode leicht zugänglich geworden ist. [8] Eine Lösung von 4 in H 2 O-gesättigtem CH 2 Cl 2 (6.9 Â 10 À4 mol L À1 ) wurde mit einer Niederdruck-Hg-Lampe 1.5 h bei Raumtemperatur unter Ar bestrahlt. Der Verlauf der Reaktion wurde dabei mittels HPLC und DC verfolgt. Die säulenchromatographische Trennung des Rohprodukts (Kieselgel; AcOEt/Hexan, 1/2) lieferte die Ausgangsverbindung 4 (45 %) und die neue Käfigverbindung 5 in Form farbloser Kristalle (7 %; Schema 1). [9] Das Massenspektrum deutete auf die Summenformel C 24 H 32 O 2 (m/z 352.2). Das Fragemtion des bezweifelt werden, dass dieses unter den physiologischen Bedingungen geöffnet wird. Eher scheint der Epoxidring als solcher chemisch unverändert an den Rezeptor zu gelangen oder ist an einer intramolekularen Wasserstoffbrückenbindung zur 3-OH-Funktion beteiligt, so dass eine günstige Konformation resultiert. [9]

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Synthetic Uses of Tosylmethyl Isocyanide (TosMIC)

Leusen

2001

Organic Reactions

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TosMIC is the acronym for 4‐tolylsulfonylmethyl isocyanide or tosylmethyl isocyanide. It is the best‐known member of a series of about 25 sulfonyl‐substituted methyl isocyanides RSO 2 CH 2 NC collected in Chart 1 (p. 426). TosMIC is a multipurpose synthetic reagent. It is by far the most versatile synthon derived from methyl isocyanide. This chapter provides a complete account of the synthetic uses of TosMIC based on a literature search closed in January 1996, and supplemented with further data available to the authors. Also included are applications of some of the more important TosMIC homologs (TosCHRNC). TosMIC is the only commercially available sulfonylmethyl isocyanide. It is a stable, colorless, practically odorless solid, which can be stored at room temperature without decomposition. Four brief review papers on the chemistry of TosMIC have appeared, in 1980, 1987, 1993, and 1995. Several reviews on the chemistry of isocyanides in general are available. An effort has been made to make this chapter as complete as possible, in coverage both by tables and by references, with respect to the immediate objective: a survey of the “Synthetic Uses of TosMIC.” Emphasis is on the primary products derived from reactions of TosMIC and related isocyanides, with limited reference to the further utilization of these products. Thus, the next section gives a complete account of reductive cyanation, the conversion of aldehydes or ketones into cyanides with the use of TosMIC, but for obvious reasons synthetic applications of the product cyanides are not treated in this chapter. One of the subsequent sections describes the application of TosMIC to the synthesis of pyrroles, including 2,3‐divinylpyrroles, which are important precursors in a new synthesis of indoles. This latter transformation, made possible by the easy availability of the precursors through TosMIC chemistry, is afforded brief coverage. As a rule, reference to preliminary papers has been omitted when the same information is available from the corresponding full papers. The patent literature is covered highly selectively and is cited only when providing new and relevant information. Negative results of reactions are reported in the text or tables only when at least some relevant information is available with respect to the conditions of such unsuccessful attempts.

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Multibridged [3_n]Cyclophanes, 1. Synthesis of [3₄](1,2,3,5)‐ and ‐(1,2,4,5)Cyclophanes

Cited by 22 publications

References 30 publications

Improved Synthesis, Structure, and Cycloaddition Reaction of [34](1,2,4,5)Cyclophane

Improved Synthesis, Structure, and Cycloaddition Reaction of [34](1,2,4,5)Cyclophane

Bildung einer neuartigen Käfigverbindung mit einem Pentacyclo[6.3.0.14,11.02,6.05,10]dodecan-Skelett durch Photolyse von [34](1,2,4,5)Cyclophan

Synthetic Uses of Tosylmethyl Isocyanide (TosMIC)

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