Total synthesis of dl-9-deoxyprostaglandin E1

Finch, Neville; Fitt, John J.; HSU, I. H. S.

doi:10.1021/jo00890a012

Cited by 66 publications

(25 citation statements)

References 11 publications

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“…After lactone ring opening with pyrrolidine and etherification of the hydroxyl group (AgO/MeI [47] ), imidazo- 2 equiv), THF, rt, 48 h. lidinone 34 was obtained, which originated 35 after hydrogenolysis (H 2 /Pd/C/HClO 4 ). Several attempts to effect the monoalkylation, namely by prior selective N-H deprotonation, gave persistently the predominant alkylation in the undesired N-1 position.…”

Section: Experimental Discussionmentioning

confidence: 99%

New Chiral Auxiliaries for Dynamic Kinetic Resolution: From Theory to Experiment

Santos¹,

Pereira²,

Afonso³

et al. 2004

Chemistry A European J

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New efficient chiral auxiliaries for dynamic kinetic resolution (DKR) of bromides into amines are proposed, based on a theoretical rationalisation of known literature results. One example was synthesized and tested, affording diastereoselectivities up to 100%. Several results of DKR reactions are known, based on oxazolidinone or imidazolidinone units as chiral auxiliaries. Nevertheless, their behaviour was not fully understood until a recent paper that we published. We now used our proposed mechanism to rationalize the behaviour of other similar chiral auxiliaries and to propose small structure changes in imidazolidinone rings which could largely improve their performance. We could show that the good performance of these molecules as chiral auxiliaries for DKR reactions where bromine is the leaving group and a primary or secondary amine is the nucleophile is due, in a first step, to the formation of a hydrogen bond between the amine and the ring carbonyl oxygen and, in a second step, to the strong electrostatic interaction between the leaving bromide and the carbonyl oxygen in the C-3 substituent. Considering the behaviour of this substituent which rotates to minimize the electrostatic repulsion with the bromide when reaching the transition state, we proposed the introduction of a second substituent in the C-4 position of the imidazolidinone ring, which prevents such rotation, thus increasing the energy difference between the transition states of the two distereoisomers. With such an auxiliary we were able to increase the best de known in literature (88%), when benzylamine is used as nucleophile, to 99, or even 100%, when iodide replaces the bromide in the substrate.

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Section: Experimental Discussionmentioning

confidence: 99%

New Chiral Auxiliaries for Dynamic Kinetic Resolution: From Theory to Experiment

Santos¹,

Pereira²,

Afonso³

et al. 2004

Chemistry A European J

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“…[13] The mixture was heated under reflux for 24 h and cooled to room temperature. The resulting solid was filtered off and the solvent was evaporated.…”

Section: Synthesis Of 57-dihydroxy-4-(methoxymethyl)coumarin (9)mentioning

confidence: 99%

“…Since structural elucidation is a significant part of our work, [8 -10] we report here the complete 13 C chemical shift assignment for a series of 6-pyranocoumarins which were divided into two groups: (i) 8H-8-oxopyran [2,3-h]coumarin (3, 5, 8 and 10) and (ii) 8H-8-oxofuro[4,3,2-de]pyrancoumarin (11)(12)(13).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and complete assignment of the ¹H and ¹³C NMR signals of some oxopyrancoumarin and oxofuropyrancoumarin derivatives

Quezada

Delogu

Viña

et al. 2008

Magnetic Reson in Chemistry

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“…The precipitated solid was filtered with suction, washed with water on the filter and airdried to give 0.73 g (74%) of 15g. Additional compounds relevant to 15b (15c, 15d) were synthesized by silver (I) oxide-mediated O-methylation 15) and conventional O-acetylation of 15b, respectively. The compounds having a difluoromethyl group (15e) and oximinomethyl group (15f) at the b-position were synthesized by the reaction of 15a with diethylaminosulfur trifluoride 16) and hydroxylamine, respectively.…”

Section: Methyl 4-cyano-1-[1-(35-dichlorophenyl)-1-methylethyl]-23-mentioning

confidence: 99%

Synthesis and Herbicidal Activity of Novel 3-Alkoxycarbonyl-3-aryl-2, 3-dihydro-2-oxo-1H-pyrrole Derivatives

et al. 2004

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Total synthesis of dl-9-deoxyprostaglandin E1

Cited by 66 publications

References 11 publications

New Chiral Auxiliaries for Dynamic Kinetic Resolution: From Theory to Experiment

New Chiral Auxiliaries for Dynamic Kinetic Resolution: From Theory to Experiment

Synthesis and complete assignment of the ¹H and ¹³C NMR signals of some oxopyrancoumarin and oxofuropyrancoumarin derivatives

Synthesis and Herbicidal Activity of Novel 3-Alkoxycarbonyl-3-aryl-2, 3-dihydro-2-oxo-1H-pyrrole Derivatives

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Total synthesis of dl-9-deoxyprostaglandin E1

Cited by 66 publications

References 11 publications

New Chiral Auxiliaries for Dynamic Kinetic Resolution: From Theory to Experiment

New Chiral Auxiliaries for Dynamic Kinetic Resolution: From Theory to Experiment

Synthesis and complete assignment of the 1H and 13C NMR signals of some oxopyrancoumarin and oxofuropyrancoumarin derivatives

Synthesis and Herbicidal Activity of Novel 3-Alkoxycarbonyl-3-aryl-2, 3-dihydro-2-oxo-1H-pyrrole Derivatives

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Synthesis and complete assignment of the ¹H and ¹³C NMR signals of some oxopyrancoumarin and oxofuropyrancoumarin derivatives