Preparation of 3e,4,5,6e,7,8-hexahydro[2.2]paracyclophane

Lin, Shaw‐Tao; Yang, Fu-May; Lin, Lee-Huey

doi:10.1016/s0040-4020(97)10031-x

Cited by 15 publications

(9 citation statements)

References 18 publications

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“…Nearly two decades later, the Ramberg–Bäcklund reaction resurfaced in synthetic work aimed at cis ‐hexahydro[2.2]paracyclophane ( 14 )19 and its trans isomer 17 20 (Scheme ). Reaction of disulfone 12 , which contains a cis ‐configured cyclohexane moiety, using Meyers’ conditions21 afforded chlorocyclophanediene 13 a (11 %).…”

Section: The Ramberg–bäcklund Reactionmentioning

confidence: 99%

Olefination Reactions in the Synthesis of Cyclophanes

Bodwell

Nandaluru

2012

Israel Journal of Chemistry

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A survey of olefination reactions that have been used in the synthesis of cyclophanes is presented. This covers the Ramberg-Bäcklund reaction, the Wittig and related reactions, the McMurry and related reactions, ring-closing metathesis (alkenes, alkynes and ene-ynes), aldol condensations and Siegrist reactions, as well as miscellaneous reactions. The McMurry reaction and ring-closing metathesis have enjoyed the greatest popularity in recent years, but they are typically used for complementary purposes. In virtually all cases, the McMurry reaction is used to install a twocarbon (1,2-ethenylene) bridge, whereas ring-closing metathesis is used to construct bridges that are at least fourmembered, but usually considerably longer. Some wellknown olefinations have seen little or no use in the field of cyclophane chemistry.The Ramberg-Bäcklund reaction [9] is the final step in a two-to three-step thioether-to-alkene conversion. As such, it appears to be well-suited for the synthesis of alkene-containing cyclophanes. Even though it applies to pre-existing cyclophanes, it warrants attention in the context of this review because both bonds of the newly formed alkene are generated during the reaction. Within the broader scope of organic synthesis, the Ramberg-Bäcklund reaction has been exploited frequently to introduce a double bond into large rings, [10] small rings [11] and more exotic ring systems such as cyclic enediynes. [12] However, it has not performed well in the synthesis of cyclophanes.The first cyclophanes to be synthesized using the Ramberg-Bäcklund reaction were the isomeric biphenylophanes (Z,Z)-7 and (E,E)-7 (Scheme 3). [13] As expected from mechanistic considerations, [14] they were formed stereospecifically in good yield (both 65 %) from the diastereomeric sulfones meso-6 and (AE)-6, respectively. Interestingly, the report of these very good results came shortly after Boekelheide wrote that "the Ramberg-Bäcklund reaction is unsatisfactory when applied to 2,11-dithia-[3.3]cyclophanes". [15] Prior to Boekelheides comment on the Ramberg-Bäcklund reaction, Martel reported that a Ramberg-Prof. Graham Bodwell obtained his B.Sc. and M.Sc. from the University of Victoria, Canada, working with Prof. Reginald Mitchell on cyclophanes. He then moved to Braunschweig, Germany, where he joined the group of Prof. Dr. Henning Hopf as a "Doktorand". Cyclophanes were also the focus of his doctoral research. He then took a break from cyclophanes and worked in the field of asymmetric synthesis as a post-doctoral fellow with Prof. Steve Davies at Oxford University. He then accepted a faculty position at Memorial University, where he now holds the rank of Professor. Cyclophanes have always been one of his core research interests.Penchal Reddy Nandaluru obtained his B.Sc. and M.Sc. from Sri Venkateswara University, India, and then worked as a chemist with AVRA Laboratories in India before joining the group of Prof. Graham Bodwell at Memorial University in St. John's, NL, Canada. The main theme of his doctoral research is the appli...

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Section: The Ramberg–bäcklund Reactionmentioning

confidence: 99%

Olefination Reactions in the Synthesis of Cyclophanes

Bodwell

Nandaluru

2012

Israel Journal of Chemistry

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“…Only one of these routes, shown in Figure 2, leads to a stable decomposition product (14), which has an energy that is about 31 kcal mol -1 lower than that of 11. The barrier to the bond breaking (94 kcal mol -1 ) is higher than the corresponding value for a standard saturated C-C bond (80 kcal mol -1 ).…”

Section: Possible Routes Of Decomposition Of 11mentioning

confidence: 99%

“…The planarization of the C6 ring could be produced by its incorporation into a macrocycle containing a benzene ring to form a cyclophane. In addition to 8 and 9, in which the planarity could be enforced by the epoxy rings, two such compounds − hexahydrogenated [2,2]paracyclophanes 10 − have been synthesized [13,14] but, for obvious reasons, the saturated ring in these cannot be planar. In this work, the spatial structure of hypothetical hexahydrosuperphane 11 is studied together with its IR spectra and NMR chemical shifts using quantum chemistry calculations.…”

Section: Introductionmentioning

confidence: 99%

Planarization of the Cyclohexane Ring by Its Incorporation Into a Cyclophane Cage: Hexahydrosuperphane

Dodziuk

Ostrowski

2006

Eur J Org Chem

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Calculations at the HF/6‐311G(d,p), DFT B3LYP/6‐311G(d,p), and MP2/6‐311G(d,p) levels show that the hypothetical molecule hexahydrosuperphane should have a planar saturated ring imposed by its incorporation into a cyclophane. The calculated NMR chemical shifts are compared with the experimental literature data for a few compounds with similar structure fragments. The calculated vibrational frequencies and the analysis of possible decomposition routes of the title molecule indicate that the molecule should be stable. Thus, it represents a plausible synthetic target. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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“…3e,4,5,6e,7,8-hexahydro[2.2]paracyclophane, 3 and 3a,4,5,6e,7,8-hexahydro[2.2]paracyclophane. 4 In our previous studies, we have also prepared the [2.2]meta-, orthoand para-cyclophanes containing either 1,4-cyclohexane or 1,3-cyclohexanes. 5 On the other hand, [2.2]-and [3.3]paracyclophanes have attracted attention in organometallic chemistry as the interaction of the two aromatic decks.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Study of Copper(I) or Silver(I) Complexes of 2,11‐Dithia‐4,5,6,7,8,9‐Hexahydro[3.3]paracyclophanes

Yang

Lin

Cao

2007

J Chinese Chemical Soc

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The complexes of 2, 11-dithia-4,5,6,7,8,9-hexahydro[3.3]paracyclophane (dthhpcp) with Cu(I), i.e. [Cu 2 I 2 (dthhpcp) 2 ]×2H 2 O 1, or with Ag(I), i.e. [Ag(dthhpcp)(NO 3 )]×thf 2 and [Ag(dthpcp)(CF 3 COO)] 3, were prepared for structural study by single-crystal X-ray diffraction analysis. For these three complexes, dthhpcp serves as a bridging group in the polymeric structure through bridging sulfur atoms via metal, while the bonding of anion with the second metal atom forms the multi-diminished structures. Complex 1 is a novel two-dimensional coordination polymer composed of Cu 6 motifs, in which Cu 2 I 2 formed a square planar unit to link the dthhpcp molecule. The two oxygen atoms of the nitrate anion as a bridge for two Ag atoms in complex 2 provides a three-dimensional channel framework of silver(I) with a tetrahydrofuran molecule as a guest inside the open cavities. In contrast, the analogous reaction with silver triflouroacetate gave a complex 3, which is composed of infinite linear chains of -Ag-dthhpcp-Ag-dthhpcp-along the a axis. Unit cell data: complex 1, orthorhombic system, space group P2 (1)2(1)2(1), a = 19.2982(11) Å b = 16.5661(10) Å, c = 25.3006(15) Å, b = 90°, Z = 8; complex 2, orthorhombic system, space group Pna2(1), a = 8.8595(6) Å, b = 12.6901(9) Å, c = 19.8449(14) Å, b = 90°, Z = 4; complex 3, monoclinic system, space group P2(1)/n, a = 8.845(3) Å, b = 20.841(6) Å, c = 11.061(3) Å, b = 107.832(6)°, Z = 4.

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Preparation of 3e,4,5,6e,7,8-hexahydro[2.2]paracyclophane

Cited by 15 publications

References 18 publications

Olefination Reactions in the Synthesis of Cyclophanes

Olefination Reactions in the Synthesis of Cyclophanes

Planarization of the Cyclohexane Ring by Its Incorporation Into a Cyclophane Cage: Hexahydrosuperphane

Synthesis and Structural Study of Copper(I) or Silver(I) Complexes of 2,11‐Dithia‐4,5,6,7,8,9‐Hexahydro[3.3]paracyclophanes

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