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Asymmetric synthesis of δ-chloro-β-amino-N-sulfinyl imidates as versatile chiral building blocks for the synthesis of 2,3-disubstituted piperidines

Elena Semina (UGent) , Filip Colpaert (UGent) , Kristof Van Hecke (UGent) , Norbert De Kimpe (UGent) and Sven Mangelinckx (UGent)
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Abstract
Mannich-type reactions of chiral delta-chloro-N-tert-butanesulfinyl-substituted imidates across N-sulfonyl aldimines resulted in the efficient and anti-stereoselective synthesis of new beta-(sulfonylamino)-N-sulfinyl imidates (dr > 99:1). These compounds were then successfully cyclized to give 2-aryl-N-sulfonylpiperidine-3-(N-sulfinyl) carbimidates in high yields. These proved to be useful intermediates for the synthesis of chiral methyl 2-arylpiperidine-3-carboxylates as well as cis-3-amino-2-aryl-N-sulfonylpiperidines.
Keywords
Chiral auxiliaries, Asymmetric synthesis, Cyclization, Diastereoselectivity, Nitrogen heterocycles, MANNICH-TYPE REACTIONS, ENANTIOSELECTIVE SYNTHESIS, SUBSTANCE-P, TERT-BUTANESULFINAMIDE, MICHAEL ADDITION, DIASTEREOSELECTIVE SYNTHESIS, STEREOSELECTIVE-SYNTHESIS, NONPEPTIDE ANTAGONIST, ACID-DERIVATIVES, NIPECOTIC ACID

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Citation

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MLA
Semina, Elena, et al. “Asymmetric Synthesis of δ-Chloro-β-Amino-N-Sulfinyl Imidates as Versatile Chiral Building Blocks for the Synthesis of 2,3-Disubstituted Piperidines.” EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, no. 22, 2015, pp. 4847–59, doi:10.1002/ejoc.201500466.
APA
Semina, E., Colpaert, F., Van Hecke, K., De Kimpe, N., & Mangelinckx, S. (2015). Asymmetric synthesis of δ-chloro-β-amino-N-sulfinyl imidates as versatile chiral building blocks for the synthesis of 2,3-disubstituted piperidines. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, (22), 4847–4859. https://doi.org/10.1002/ejoc.201500466
Chicago author-date
Semina, Elena, Filip Colpaert, Kristof Van Hecke, Norbert De Kimpe, and Sven Mangelinckx. 2015. “Asymmetric Synthesis of δ-Chloro-β-Amino-N-Sulfinyl Imidates as Versatile Chiral Building Blocks for the Synthesis of 2,3-Disubstituted Piperidines.” EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, no. 22: 4847–59. https://doi.org/10.1002/ejoc.201500466.
Chicago author-date (all authors)
Semina, Elena, Filip Colpaert, Kristof Van Hecke, Norbert De Kimpe, and Sven Mangelinckx. 2015. “Asymmetric Synthesis of δ-Chloro-β-Amino-N-Sulfinyl Imidates as Versatile Chiral Building Blocks for the Synthesis of 2,3-Disubstituted Piperidines.” EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (22): 4847–4859. doi:10.1002/ejoc.201500466.
Vancouver
1.
Semina E, Colpaert F, Van Hecke K, De Kimpe N, Mangelinckx S. Asymmetric synthesis of δ-chloro-β-amino-N-sulfinyl imidates as versatile chiral building blocks for the synthesis of 2,3-disubstituted piperidines. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY. 2015;(22):4847–59.
IEEE
[1]
E. Semina, F. Colpaert, K. Van Hecke, N. De Kimpe, and S. Mangelinckx, “Asymmetric synthesis of δ-chloro-β-amino-N-sulfinyl imidates as versatile chiral building blocks for the synthesis of 2,3-disubstituted piperidines,” EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, no. 22, pp. 4847–4859, 2015.
@article{6923924,
  abstract     = {{Mannich-type reactions of chiral delta-chloro-N-tert-butanesulfinyl-substituted imidates across N-sulfonyl aldimines resulted in the efficient and anti-stereoselective synthesis of new beta-(sulfonylamino)-N-sulfinyl imidates (dr > 99:1). These compounds were then successfully cyclized to give 2-aryl-N-sulfonylpiperidine-3-(N-sulfinyl) carbimidates in high yields. These proved to be useful intermediates for the synthesis of chiral methyl 2-arylpiperidine-3-carboxylates as well as cis-3-amino-2-aryl-N-sulfonylpiperidines.}},
  author       = {{Semina, Elena and Colpaert, Filip and Van Hecke, Kristof and De Kimpe, Norbert and Mangelinckx, Sven}},
  issn         = {{1434-193X}},
  journal      = {{EUROPEAN JOURNAL OF ORGANIC CHEMISTRY}},
  keywords     = {{Chiral auxiliaries,Asymmetric synthesis,Cyclization,Diastereoselectivity,Nitrogen heterocycles,MANNICH-TYPE REACTIONS,ENANTIOSELECTIVE SYNTHESIS,SUBSTANCE-P,TERT-BUTANESULFINAMIDE,MICHAEL ADDITION,DIASTEREOSELECTIVE SYNTHESIS,STEREOSELECTIVE-SYNTHESIS,NONPEPTIDE ANTAGONIST,ACID-DERIVATIVES,NIPECOTIC ACID}},
  language     = {{eng}},
  number       = {{22}},
  pages        = {{4847--4859}},
  title        = {{Asymmetric synthesis of δ-chloro-β-amino-N-sulfinyl imidates as versatile chiral building blocks for the synthesis of 2,3-disubstituted piperidines}},
  url          = {{http://doi.org/10.1002/ejoc.201500466}},
  year         = {{2015}},
}

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