Synthesis of 1,2,9,10-tetrahydroxy[2.2]metacyclophanes via pinacol coupling reaction of 1,3-benzenedicarboxyaldehydes

Sahade, Daniel A.; Tsukamoto, Ken ichi; Thiemann, Thies; Sawada, Tsuyoshi; Mataka, Shuntarō

doi:10.1016/s0040-4020(99)00055-1

Cited by 12 publications

(3 citation statements)

References 14 publications

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“…In an attempt to circumvent the failed sulfide coupling, the use of a 2-fold intramolecular McMurry reaction was briefly investigated. Despite its generally poor record in the synthesis of [2.2]metacyclophanes, intramolecular McMurry reactions have recently been applied successfully. , Tetraester 21a was therefore reduced with LiAlH 4 , and the crude tetraol was oxidized with PCC to afford the corresponding tetraaldehyde (34%, two steps) (Scheme ). Subjection of this compound to McMurry reaction conditions resulted in the complete consumption of the starting material, but no mobile compounds, e.g.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Crystal Structure, and Resolution of [10](1,6)Pyrenophane: An Inherently Chiral [n]Cyclophane

et al. 2011

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A synthetic approach to a set of three inherently chiral [n]cyclophanes, [n](1,6)pyrenophanes (29a-c, n = 8-10) was investigated. Progress toward 29a was thwarted by the failure of the key dithiacyclophane-forming reaction. For the next higher homologue, the synthesis was completed, but the desired [9](1,6)pyrenophane (29b) could only be partially separated from an isomeric pyrenophane, [9](1,8)pyrenophane (28b), and an unidentified byproduct. Work aimed at the synthesis of the next higher homologue resulted in the isolation of a 7:4 mixture of [10](1,8)pyrenophane (28c) and [10](1,6)pyrenophane (29c), which could not be separated by column chromatography or crystallization. However, single-crystal X-ray structures of 28c and 29c were obtained after manual separation of two crystals with different morphologies from the same batch of crystals obtained from the 7:4 mixture of 28c and 29c. The pyrene system of 29c was found to have a gentle end-to-end bend as well as a significant longitudinal twist. Short intermolecular C(sp(3))-H···π contacts (2.64 to 2.76 Å) between H-atoms on the bridge and the centroids of three of the four six-membered rings of the pyrene system of a neighboring pyrenophane of like chirality give rise to the formation of single enantiomer columns. From a DNMR study of the mixture of 28c and 29c, the bridge in [10](1,8)pyrenophane (28c) was found to undergo a conformational flip from one side of the pyrene system to the other with ΔG(‡) = 14.9 ± 0.2 kcal/mol. A two-stage preparative HPLC protocol was subsequently developed for the separation of 28c and 29c (Chiralpak AD-H column) and then the enantiomers of 29c (Chiralcel OJ-H column). This enabled the measurement of their optical rotations and CD spectra.

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Section: Resultsmentioning

confidence: 99%

Synthesis, Crystal Structure, and Resolution of [10](1,6)Pyrenophane: An Inherently Chiral [n]Cyclophane

et al. 2011

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“…In 2008, we have reported new synthetic method of DHP (Scheme 2) [17]. Tetrahydroxy-[2.2]MCP 12 was prepared from benzene-dialdehyde derivative 11 in one step [21,22]. The MCP 12 has the potential to be the intermediate of DHPs, because the MCP 6 has two trans-diols at its both bridge positions and their reduction could give a MCPD, which is an equivalent of DHP 9.…”

Section: Preparation Of Parent Dhpmentioning

confidence: 99%

Chirality and Circular Polarized Properties of Photochromic Polyaromatic Molecules

Sawada¹,

Kubo²,

Nanamura³

2019

Chirality From Molecular Electronic States

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Dihydropyrenes (DHPs) are a particularly interesting class of photochromic polyaromatic molecules due to their negative photochromism in UV-Vis spectra. Asymmetric heterocyclic-[e]-annelated DHPs were prepared by new synthetic routes and their photochromism was studied. The optical resolution of heterocyclic-[e]-annelated DHPs was performed by chiral HPLC systems and their enantiomers indicate the photochromism for UV-Vis, and CD spectra. The absolute structures of the enantiomers were determined by using spectra predicted with time-dependent density functional theory. Photoswitchable circular dichroism properties of asymmetric heterocyclic-[e]-annelated DHPs have potential as the molecular device to control the circular polarized light.

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“…Previously, we have reported the development of a pinacol coupling method to yield [2.2]metacyclophanes (MCPs) that have pinacol units . Pinacols widely occur in many biologically active molecules such as Taxol4a and (−)-grayanotoxin III 4b.…”

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confidence: 99%

Novel Calixarene Hemisphere Synthesized via Pinacol Rearrangement of [2.1.2.1]Metacyclophane

et al. 2006

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[reaction: see text] Tetramethoxy[2.1.2.1]metacyclophane ([2.1.2.1]MCP) was prepared by the pinacol coupling reaction of diphenylmethane dialdehyde. The treatment of [2.1.2.1]MCP with trimethylsilyl chloride and sodium iodide yielded two unexpected calixarene derivatives, cone (hemisphere) and 1,2-alternate types, instead of octahydroxy[2.1.2.1]MCP. The X-ray structure of the cone-type derivative and its inclusion property with acetonitrile were also discussed.

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Synthesis of 1,2,9,10-tetrahydroxy[2.2]metacyclophanes via pinacol coupling reaction of 1,3-benzenedicarboxyaldehydes

Cited by 12 publications

References 14 publications

Synthesis, Crystal Structure, and Resolution of [10](1,6)Pyrenophane: An Inherently Chiral [n]Cyclophane

Synthesis, Crystal Structure, and Resolution of [10](1,6)Pyrenophane: An Inherently Chiral [n]Cyclophane

Chirality and Circular Polarized Properties of Photochromic Polyaromatic Molecules

Novel Calixarene Hemisphere Synthesized via Pinacol Rearrangement of [2.1.2.1]Metacyclophane

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