Asymmetric reactions. XLV. Utilisation of the asymmetric transformation to determine the absolute configuration of amines

Červinka, O.; Dudek, V.

doi:10.1135/cccc19731159

“…This result was confirmed after removal of the sulfonimidoyl moiety from ent ‐ 4 a . The free amine 18 , whose optical rotation corresponds to the S isomer,24 was produced in 84 % yield by using sodium naphthanelide in THF at room temperature; whereas, application of these conditions to 4 a afforded ( R )‐ 18 , as indicated by the opposite optical rotation (Scheme ). Importantly, chiral HPLC indicated that removal of the sulfonimidoyl group takes place without epimerization at the benzylic center.…”

Section: Methodsmentioning

confidence: 99%

Efficient Diastereoselective Intermolecular Rhodium‐Catalyzed CH Amination

Liang¹,

Robert‐Peillard²,

Fruit³

et al. 2006

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The selective functionalization of a CÀH bond is an area of intense investigation as such a reaction leads to the formation of valuable building blocks from simple molecules.[1] Considering the ubiquity of CÀH bonds in organic compounds, the search for a process that allows their selective transformation remains challenging. Methodologies have been recently developed for regioselective CÀC, [2] CÀO, [3] or CÀN [4,5] bond formations that have found applications in total synthesis. [6] In the case of CÀH amination, significant results have been obtained by using transition-metal-catalyzed nitrene transfer that starts from iminoiodanes. [5,7] This field, pioneered by Breslow [8] and Mansuy, [9] has progressed considerably over the last five years with the discovery of new methodologies for the generation [5a,d, 10] of these hypervalent iodine(III) reagents in situ. Thus, PhI(OAc) 2 -mediated CÀH amination has been shown to be catalyzed by ruthenium,

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“…Corresponding cis-(+) compound 12 (glc 98.5%, [cv)25d +46.2°) was obtained similarly, starting from 7c. c is-(± )-3-Methyl-1-( 1-methyl-2-phenylethyl)-A-phenyl-4piperidineamine Dihydrochloride (13). A mixture of 7a (5.7 g. 0.03 mol), l-methyl-2-phenylethanol methanesulfonate (7 g, 0.033 mol), and Na2C03 (8 g, 0.075 mol) in ¿-BuCOMe (300 ml) was stirred and refluxed for 48 hr.…”

Section: Methodsmentioning

confidence: 99%

“…CL ''Assuming that 13 contains a 1:1 ratio of K3 and K2. mixture (± 1:1) of czs-3-methyl-l-(l-methyl-2-phenylethyl)-iV-phenylpiperidineamine (13). Attempts to separate the mixture by fractional crystallization or with the aid of column chromatography failed, partly owing to instability of dihydrochloride salt 13.…”

mentioning

confidence: 99%

Synthetic analgesics. Synthesis and pharmacology of the diastereoisomers of N-[3-methyl-1-(2-phenylethyl)-4-piperidyl]-N-phenylpropanamide and N-[3-methyl-1-(1-methyl-2-phenylethyl)-4-piperidyl]-N-phenylpropanamide

Bever¹,

Niemegeers²,

Janßen³

1974

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The antagonistic property of ethyl p-(4-ethoxycarbonyl-4-phenyl-l-piperidinoethyl)fumaranilate ( 5) was investigated. Compound 5 was found to antagonize morphine analgesia in a complex manner which could not be described as a simple competitive or noncompetitive type. The antagonism, however, lasted for over 6 hr suggesting that 5 has a high affinity for the analgesic receptors. Compound 5 appeared to possess dependence liability in the single-dose suppression test. In the electrically stimulated isolated guinea pig ileum, 5 acted like an agonist. No antagonistic activity of 5 was apparent in the latter two tests.

show abstract

Efficient Diastereoselective Intermolecular Rhodium‐Catalyzed CH Amination

Liang

¹

,

Robert‐Peillard

²

,

Fruit

³

et al. 2006

View full text Add to dashboard Cite

The selective functionalization of a CÀH bond is an area of intense investigation as such a reaction leads to the formation of valuable building blocks from simple molecules.[1] Considering the ubiquity of CÀH bonds in organic compounds, the search for a process that allows their selective transformation remains challenging. Methodologies have been recently developed for regioselective CÀC, [2] CÀO, [3] or CÀN [4,5] bond formations that have found applications in total synthesis. [6] In the case of CÀH amination, significant results have been obtained by using transition-metal-catalyzed nitrene transfer that starts from iminoiodanes. [5,7] This field, pioneered by Breslow [8] and Mansuy, [9] has progressed considerably over the last five years with the discovery of new methodologies for the generation [5a,d, 10] of these hypervalent iodine(III) reagents in situ. Thus, PhI(OAc) 2 -mediated CÀH amination has been shown to be catalyzed by ruthenium,

show abstract

Asymmetric reactions. XLV. Utilisation of the asymmetric transformation to determine the absolute configuration of amines

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Efficient Diastereoselective Intermolecular Rhodium‐Catalyzed CH Amination

Efficient Diastereoselective Intermolecular Rhodium‐Catalyzed CH Amination

Synthetic analgesics. Synthesis and pharmacology of the diastereoisomers of N-[3-methyl-1-(2-phenylethyl)-4-piperidyl]-N-phenylpropanamide and N-[3-methyl-1-(1-methyl-2-phenylethyl)-4-piperidyl]-N-phenylpropanamide

Efficient Diastereoselective Intermolecular Rhodium‐Catalyzed CH Amination

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