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80053525583
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From the hydrogenation product the THP ether of the 4-amino-2(R)- methylbutan-1-ol, an important intermediate towards the receptor antagonist TAK-637, can be synthesized
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A. Preetz C. Fischer C. Kohrt H.-J. Drexler W. Baumann D. Heller Organometallics 2011 30 5155 5159
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80052054192
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[2-(3-Methoxy-phenyl)-cyclohex-1-enylmethyl]-dimethylamine is a member of a class of 1,2-disubstituded cyclohexene derivatives which are important intermediates in the synthesis of pharmaceutically active compounds acting on the central nervous system. The challenge is the establishment of the desired relative and absolute stereochemistry of two new stereogenic centers responsible for the pharmacological effect. [2-(3-Methoxy-phenyl)-cyclohex-1-enylmethyl]- dimethylamine can be transformed by a stereoselective hydrogenation to Tramadol, an important analgesic drug used world-wide Elemental analysis of a saturated NaCl solution in methanol showed that in 1.0 mL MeOH ca. 7 mg of NaCl can be dissolved, which corresponds to 0.12 mmol. 105 mg NaBr (1.0 mmol) and 496 mg NaI (3.3 mmol) can be dissolved in 1.0 mL MeOH
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C. A. Busacca D. R. Fandrick J. J. Song C. H. Senanayake Adv. Synth. Catal. 2011 353 1825 1864
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A. Preetz H.-J. Drexler C. Fischer Z. Dai A. Börner W. Baumann A. Spannenberg R. Thede D. Heller Chem.-Eur. J. 2008 14 1445 1451
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19
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84872529648
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in preparation The dinuclear complex is very soluble in THF, however scarcely soluble in MeOH. Vice versa, the trinuclear complex is more soluble in MeOH than in THF
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A. Meißner, A. Preetz, H.-J. Drexler, W. Baumann, A. Spannenberg, A. König and D. Heller, in preparation
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20
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67650293102
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All attempts to isolate [Rh3(t-Bu-BisP*) 3(μ3-Cl)2][BF4] from the reaction of the solvate complex with NaCl failed. However, we succeeded while trying to isolate the product complex [Rh(t-Bu-BisP*)(macH2)][BF 4] from CH2Cl2: the hydrogenation product of mac was added to the solvate MeOH complex. The solvent was removed in vacuo and the remaining solid was redissolved in CH2Cl2 and layered with diethyl ether. After a few days single crystals of [Rh3(t-Bu- BisP*)3(μ3-Cl)2][BF4] suitable for X-ray analysis crystallized
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A. Preetz W. Baumann C. Fischer H.-J. Drexler T. Schmidt R. Thede D. Heller Organometallics 2009 28 3673 3677
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Heller, D.7
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21
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84863304115
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The molecular structure of the trinuclear complex obtained in a different way is shown in Fig. S8, ESI The μ3-bridges of the trinuclear complex are disordered (population: 0.6 Cl, 0.4 Br). The only Cl source can be the solvent CH2Cl2 from which the complex was recrystallized. Only one of the four possible populations is shown
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C. Kohrt S. Hansen H.-J. Drexler U. Rosenthal A. Schulz D. Heller Inorg. Chem. 2012 51 7377 7383
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Heller, D.6
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The asymmetric hydrogenation of dimethyl itaconate as well as the structure and stability of the catalyst-substrate complex with the DIPAMP system are described in
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The prochiral olefin (Z)-3-[1-(dimethylamino)-2-methylpent-2-en-3-yl] phenol is also an important precursor of the new analgesic drug Tapentadol which is as an open-chain analogue of Tramadol. The chirality of the new stereogenic centers is very important for the pharmacological effect. The (R,R) stereoisomer of Tapentadol is a novel, centrally acting analgesic with a dual mode of action: μ-opioid receptor (MOR) agonism and norepinephrine reuptake inhibition. Tapentadol is the first oral centrally acting analgesic to be approved in 2008 in the United States for more than a decade. The corresponding (S,S) enantiomer is a very strong opioid. The (R,S) or (S,R) stereoisomers have no analgesic effect
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K. G. Moloy J. L. Petersen Organometallics 1995 14 2931 2936
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