15991-59-0Relevant academic research and scientific papers
Stereoselective total synthesis of the piperidine alkaloids, (+)-coniine, (+)-pseudoconhydrine, and (+)-sedamine through a common intermediate
Satyalakshmi, Gandham,Suneel, Kanaparthy,Shinde, Digambar Balaji,Das, Biswanath
, p. 1000 - 1005 (2011)
The stereoselective total synthesis of the piperidine alkaloids, (+)-coniine, (+)-pseudoconhydrine and (+)-sedamine has been achieved through a common intermediate generated from butane-1,4-diol. The synthetic sequence involves a Maruoka asymmetric allylation and ring-closing metathesis as the key steps.
Enantioselective Rhodium-Catalyzed Allylation of Aliphatic Imines: Synthesis of Chiral C Aliphatic Homoallylic Amines
Li, Wei-Sian,Kuo, Ting-Shen,Hsieh, Meng-Chi,Tsai, Ming-Kang,Wu, Ping-Yu,Wu, Hsyueh-Liang
supporting information, p. 5675 - 5679 (2020/08/10)
Reported herein is a method for the efficient syntheses of optically active 1-alkyl homoallylic amines in yields up to 95%, 13.5:1 dr, and 98% ee under mild, aqueous reaction conditions, via the Rh-catalyzed asymmetric allylation of aliphatic aldimines. This method provides a streamlined synthetic platform for the preparation of indolizidine and piperidine alkaloids, thus demonstrating its usefulness.
Rhodium-Catalyzed Asymmetric Intramolecular Hydroamination of Allenes
Berthold, Dino,Geissler, Arne G. A.,Giofré, Sabrina,Breit, Bernhard
supporting information, p. 9994 - 9997 (2019/07/04)
The rhodium-catalyzed asymmetric intramolecular hydroamination of sulfonyl amides with terminal allenes is reported. It provides selective access to 5- and 6-membered N-heterocycles, scaffolds found in a large range of different bioactive compounds. Moreover, gram scale reactions, as well as the application of suitable product transformations to natural products and key intermediates thereof are demonstrated.
Regio- and Stereoselective Alkylation of Pyridine-N-oxides: Synthesis of Substituted Piperidines and Pyridines
Barange, Deepak Kumar,Johnson, Magnus T.,Cairns, Andrew G.,Olsson, Roger,Almqvist, Fredrik
supporting information, p. 6228 - 6231 (2016/12/23)
Regio- and stereoselective addition of alkyl Grignard reagents to pyridine-N-oxides gave C2-alkylated N-hydroxy-1,2,5,6-tetrahydropyridines and trans-2,3-disubstituted N-hydroxy-1,2,5,6-tetrahydropyridines in good to excellent yields. These intermediates were aromatized or alternatively reduced in one-pot methodologies for efficient syntheses of alkylpyridines or piperidines, respectively. These reactions have a broad substrate scope and short reaction times.
Synthesis of optically active heterocyclic compounds via deracemization of 1,2-diol monotosylate derivatives bearing a long aliphatic chain by a combination of enzymatic hydrolysis with Mitsunobu inversion
Matsumoto, Kazutsugu,Usuda, Kazumasa,Okabe, Hirokazu,Hashimoto, Manabu,Shimada, Yasutaka
, p. 108 - 115 (2013/04/23)
We have succeeded in accomplishing the deracemization of (±)-2-acetoxydecyl and (±)-acetoxy-6-benzyloxyhexyl tosylates, which have a long substituent, via an enzyme-mediated enantioselective hydrolysis with a Mitsunobu inversion using polymer-supported triphenylphosphine to afford the corresponding (S)-enantiomer. Enantiomerically pure (S)- and (R)-γ-dodecalactones, a fruit flavor, were synthesized from (S)-2-acetoxydecyl tosylate as the mutual starting material. The poisonous alkaloid (S)-coniine was also synthesized using enantiomerically pure allyl amine as the key intermediate derived from (S)-acetoxy-6-benzyloxyhexyl tosylate.
A direct and general method for the reductive alkylation of tertiary lactams/amides: Application to the step economical synthesis of alkaloid (-)-morusimic acid D
Xiao, Kai-Jiong,Wang, Yu,Huang, Ying-Hong,Wang, Xiao-Gang,Huang, Pei-Qiang
, p. 8305 - 8311 (2013/09/24)
Full details of the direct and general method for the reductive alkylation of tertiary lactams and amides to give tertiary sec-alkylamines are presented. This one-pot method consists of in situ activation of a lactam or an amide with Tf2O/DTBMP, addition of a Grignard reagent, and reduction of the resulting iminium intermediates. Alkyl, benzyl, and aryl Grignard reagents and several reductants or reducing conditions (LiAlH4, NaBH4, Hantzsch ester, Bu3SnH, Pd(OH)2/C, H2) could be used effectively. Reductive alkylations of substituted lactams demonstrated good to excellent 1,3-asymmetric induction to provide the corresponding di- or trisubstituted pyrrolidine/piperidine in 6:1 (LiAlH4), 11:1 (Et 3SiH), and 20:1 (catalytic hydrogenation) cis/trans diastereoselectivity, respectively. The versatility of this methodology was demonstrated by its application in the concise stereoselective synthesis of piperidine alkaloid (-)-morusimic acid.
A [3+3] cyclization strategy for asymmetric synthesis of alkyl substituted piperidine-2-ones using 1,2-cyclic sulfamidates: A formal synthesis of (S)-coniine from l-norvaline
Karanfil, Abdullah,Balta, Berrin,Eskici, Mustafa
, p. 10218 - 10229,12 (2020/09/02)
Regioselective ring-opening reactions of a set of representative 1,2-cyclic sulfamidates with lithium triethylorthopropiolate proceeded efficiently to deliver the corresponding δ-amino-α,β-unsaturated esters after acidic hydrolysis. Hydrogenation of the unsaturated esters and subsequent thermal cyclization afforded the related alkyl substituted piperidine-2-ones. This approach represents a novel [3+3] cyclization strategy for the asymmetric synthesis of alkyl substituted piperidin-2-ones. Efficiency of the cyclization process is illustrated by a formal asymmetric synthesis of (S)-coniine from l-norvaline.
Straightforward access to enantioenriched 2-allylpiperidine: Application to the synthesis of alkaloids
Bosque, Irene,González-Gómez, José C.,Foubelo, Francisco,Yus, Miguel
, p. 780 - 784 (2012/03/26)
An efficient stereocontrolled preparation of (2R,RS)-2-allyl-(N- tert-butylsulfinyl)piperidine and its enantiomer is detailed. The sequence requires only two synthetic operations with one-column chromatography and is readily scaled up. The versatility of these chiral building blocks was exemplified by the total or formal synthesis of some natural and unnatural alkaloids.
Gold(I)-catalyzed intramolecular amination of allylic alcohols with alkylamines
Mukherjee, Paramita,Widenhoefer, Ross A.
, p. 1334 - 1337 (2011/05/15)
A 1:1 mixture of (1)AuCl [1 = P(t-Bu)2o-biphenyl] and AgSbF 6 catalyzes the intramolecular amination of allylic alcohols with alkylamines to form substituted pyrrolidine and piperidine derivatives. Gold(I)-catalyzed cyclization of (R,Z)-8-(N-benzylamino)-3-octen-2-ol (96% ee, 95% de) led to isolation of (R,E)-1-benzyl-2-(1-propenyl)piperidine in 99% yield with 96% ee, consistent with the net syn addition of the amine relative to the departing hydroxyl group.
Asymmetric synthesis of piperidines and octahydroindolizines using a one-pot ring-closure/N-debenzylation procedure
Davies, Stephen G.,Fletcher, Ai M.,Hughes, Deri G.,Lee, James A.,Price, Paul D.,Roberts, Paul M.,Russell, Angela J.,Smith, Andrew D.,Thomson, James E.,Williams, Oliver M.H.
, p. 9975 - 9992 (2012/02/15)
The conjugate addition of an enantiopure lithium amide to a ζ-hydroxy-α,β-unsaturated ester followed by a one-pot ring-closure/N-debenzylation protocol has been used in the asymmetric syntheses of (S)-coniine and (R)-δ-coniceine (isolated as the corresponding hydrochloride salts), and (R,R)-1-(hydroxymethyl)octahydroindolizine (the bicyclic fragment of stellettamides A-C).
