Asymmetric Synthesis of (+)-L-733, 060 and (+)-CP-99, 994 Based on a New Chiral 3-Piperidinol Synthon

Huang, Pei‐Qiang; Liu, Liangxian; Wei, Bang‐Guo; Ruan, Yuan‐Ping

doi:10.1021/ol034505g

Cited by 83 publications

(18 citation statements)

References 24 publications

(16 reference statements)

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“…In recent years, we have been engaged in the development of protected 3-hydroxyglutarimides 8-based synthetic methodologies [14][15][16]. The value of this chiral building block is being demonstrated by our group [17][18][19][20][21][22][23][24], and also by other research groups [25][26][27][28].…”

Section: Introductionmentioning

confidence: 98%

Asymmetric syntheses of (8R,8aS)- and (8R,8aR)-8-hydroxy-5-indolizidinones: Two promising oxygenated indolizidine building blocks

Zhang

Huang

et al. 2011

Sci. China Chem.

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Starting from the oxygenated piperidine building block 20, two synthetic approaches to new building blocks (8R,8aS)- and (8R,8aR)-8-hydroxy-5-indolizidinones 19a/19b and 15a/15b have been developed, respectively. The first one is based on the trans-diastereoselective reductive alkylation (dr = 93:7), followed by a four-step procedure; and the second one called for the RCM reaction on the N,O-acetal derived from a vinylation, which was followed by a pyrrole formation, and a stereocontrolled cis-selective (dr = 91:9) catalytic hydrogenation. Reduction of the diastereomer 15a produced (8R,8aR)-8-indolizidinol (18).NSF of China[20672089, 20832005]; NFFTBS[J1030415]; National Basic Research Program of China[2010CB833200

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Section: Introductionmentioning

confidence: 98%

Asymmetric syntheses of (8R,8aS)- and (8R,8aR)-8-hydroxy-5-indolizidinones: Two promising oxygenated indolizidine building blocks

Zhang

Huang

et al. 2011

Sci. China Chem.

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“…Potassium tert-butoxide catalysed rearrangement of 18 provided glutarimide 19 in high yield (90%). 8 The C2 carbonyl group of 19 was regioselectively reduced using NaBH 4 to give the diol 2a. 9 With the cyclization precursor in hand we further subjected 2a to various Lewis acid or acid catalysed reaction conditions.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of spirocyclic azacycles from the cyclization of furan tethered N-acyliminium ions

2012

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The protic and Lewis acid promoted cyclization reactions of tethered furan-4,5-dihydroxypiperid-2-ones, furan-4,5-diacetoxypiperid-2-ones and furan-3,4-diacetoxypyrrolid-2-ones, via their corresponding Nacyliminium ion intermediates, have been studied. In the case of the furan-4,5-dihydroxypiperid-2-one 2a and its diacetate derivative 2b, macrocyclic products were formed from an initial intermolecular reaction between 2a or 2b, via the nucleophilic C5 furan carbon, and their corresponding N-acyliminium ion intermediates. When the furan C5 position of 2b was blocked by substitution with bromine then TFA or Sc(OTf)3 catalysed cyclization reactions gave a spirotricyclic product (a 5-6-6-tricycle) in a highly diastereoselective manner. Cyclization of the analogous C5-Br-furan-pyrrolidone 29 with TFA resulted in a related spirotricyclic (a 5-6-5 tricycle) product. Attempts to prepare an analogous azepine system, a 5-7-5 tricycle, were not successful. Cyclization reactions of the C5-PhS-furan-or C5-phenylsulfonyl-pyrrolidone analogues of 29 with TFA were also not successful. Cyclization of the analogous C5-Br-furan-pyrrolidone 29 with TFA resulted in a related spirotricyclic (a 5-6-5 tricycle) product. Attempts to prepare an analogous azepine system, a 5-7-5 tricycle, were not successful. Cyclization reactions of the C5-PhS-furanor C5-phenylsulfonyl-pyrrolidone analogues of 29 with TFA were also not successful.2

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“…Among a great deal of valuable methods developed for their construction [5][6][7][8][9][10] , those using L-glutamic acid as a chiron have attracted much attention [11][12][13][14][15][16][17][18][19][20][21][22][23][24] . For the introduction of the required C-2 or C-6 substituents, the methods based on the iminium ion/N-acyliminium ion [25][26][27][28][29][30][31][32][33] intermediates are quite popular.…”

Section: Introductionmentioning

confidence: 99%

Generation and α-hydroxyalkylation of a novel 3-piperidinol N-α-carbanion intermediate

Zheng

Guo

Ruan

et al. 2009

Sci. China Ser. B-Chem.

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The (S)-sulfide 6 has been synthesized as a synthetic equivalent of novel 3-piperidinol N-α-carbanion B via deprotonation and lithium naphthanelide (LN)-mediated reductive lithiation. The reaction of the 3-piperidinol N-α-carbanion intermediate B with carbonyl compounds gave, besides some reduced product 2a, the desired α-hydroxyalkylation products 12-17 with excellent 2,3-diastereoselectivity. The reductive α-hydroxyalkylation with unsymmetric carbonyl compounds led to only 50:50 to 77:23 diastereoselectivities at the C-1' carbinol center.

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Asymmetric Synthesis of (+)-L-733, 060 and (+)-CP-99, 994 Based on a New Chiral 3-Piperidinol Synthon

Cited by 83 publications

References 24 publications

Asymmetric syntheses of (8R,8aS)- and (8R,8aR)-8-hydroxy-5-indolizidinones: Two promising oxygenated indolizidine building blocks

Asymmetric syntheses of (8R,8aS)- and (8R,8aR)-8-hydroxy-5-indolizidinones: Two promising oxygenated indolizidine building blocks

Synthesis of spirocyclic azacycles from the cyclization of furan tethered N-acyliminium ions

Generation and α-hydroxyalkylation of a novel 3-piperidinol N-α-carbanion intermediate

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