Publication

Oxa-Michael Addition to alpha,beta-Unsaturated Nitriles: An Expedient Route to gamma-Amino Alcohols and Derivatives

Guo, B., Zijlstra, D. S., de Vries, J. G. & Otten, E., 9-Jul-2018, In : ChemCatChem. 10, 13, p. 2868-2872 5 p.

Research output: Contribution to journalArticleAcademicpeer-review

APA

Guo, B., Zijlstra, D. S., de Vries, J. G., & Otten, E. (2018). Oxa-Michael Addition to alpha,beta-Unsaturated Nitriles: An Expedient Route to gamma-Amino Alcohols and Derivatives. ChemCatChem, 10(13), 2868-2872. https://doi.org/10.1002/cctc.201800509

Author

Guo, Beibei ; Zijlstra, Douwe S. ; de Vries, Johannes G. ; Otten, Edwin. / Oxa-Michael Addition to alpha,beta-Unsaturated Nitriles : An Expedient Route to gamma-Amino Alcohols and Derivatives. In: ChemCatChem. 2018 ; Vol. 10, No. 13. pp. 2868-2872.

Harvard

Guo, B, Zijlstra, DS, de Vries, JG & Otten, E 2018, 'Oxa-Michael Addition to alpha,beta-Unsaturated Nitriles: An Expedient Route to gamma-Amino Alcohols and Derivatives', ChemCatChem, vol. 10, no. 13, pp. 2868-2872. https://doi.org/10.1002/cctc.201800509

Standard

Oxa-Michael Addition to alpha,beta-Unsaturated Nitriles : An Expedient Route to gamma-Amino Alcohols and Derivatives. / Guo, Beibei; Zijlstra, Douwe S.; de Vries, Johannes G.; Otten, Edwin.

In: ChemCatChem, Vol. 10, No. 13, 09.07.2018, p. 2868-2872.

Research output: Contribution to journalArticleAcademicpeer-review

Vancouver

Guo B, Zijlstra DS, de Vries JG, Otten E. Oxa-Michael Addition to alpha,beta-Unsaturated Nitriles: An Expedient Route to gamma-Amino Alcohols and Derivatives. ChemCatChem. 2018 Jul 9;10(13):2868-2872. https://doi.org/10.1002/cctc.201800509


BibTeX

@article{a73452196c404ad4a28a94c934fcb906,
title = "Oxa-Michael Addition to alpha,beta-Unsaturated Nitriles: An Expedient Route to gamma-Amino Alcohols and Derivatives",
abstract = "Water addition to alpha,beta-unsaturated nitriles would give facile access to the -hydroxy-nitriles, which in turn can be hydrogenated to the gamma-amino alcohols. We have previously shown that alcohols readily add in 1,4-fashion to these substrates using Milstein's Ru(PNN) pincer complex as catalyst. However, attempted water addition to alpha,beta-unsaturated nitriles gave the 3-hydroxynitriles in mediocre yields. On the other hand, addition of benzyl alcohol proceeded in excellent yields for a variety of -substituted unsaturated nitriles. Subsequent treatment of the benzyl alcohol addition products with TMSCl/FeCl3 resulted in the formation of 3-hydroxy-alkylnitriles. The 3-benzyloxy-alkylnitriles obtained from oxa-Michael addition also could be hydrogenated directly in the presence of acid to give the amino alcohols as their HCl salts in excellent yields. Hydrogenation under neutral conditions gave a mixture of the secondary and tertiary amines. Hydrogenation in the presence of base and Boc-anhydride gave the orthogonally bis-protected amino alcohols, in which the benzyl ether can subsequently be cleaved to yield Boc-protected amino alcohols. Thus, a variety of molecular scaffolds with a 1,3-relationship between O- and N-functional group is accessible starting from oxa-Michael addition of benzyl alcohol to alpha,beta-unsaturated nitriles.",
keywords = "oxa-Michael addition, amino alcohols, hydrogenation, nitriles, pincer ligand, ruthenium, ENANTIOSELECTIVE BETA-BORYLATION, REDOX-FLOW BATTERY, TRIETHANOLAMINE STEARATE, UNSATURATED NITRILES, CARBOXYLIC-ACIDS, LIGAND, WATER, ACCEPTORS, COMPLEX, HYDROGENATION",
author = "Beibei Guo and Zijlstra, {Douwe S.} and {de Vries}, {Johannes G.} and Edwin Otten",
year = "2018",
month = "7",
day = "9",
doi = "10.1002/cctc.201800509",
language = "English",
volume = "10",
pages = "2868--2872",
journal = "ChemCatChem",
issn = "1867-3880",
publisher = "WILEY-V C H VERLAG GMBH",
number = "13",

}

RIS

TY - JOUR

T1 - Oxa-Michael Addition to alpha,beta-Unsaturated Nitriles

T2 - An Expedient Route to gamma-Amino Alcohols and Derivatives

AU - Guo, Beibei

AU - Zijlstra, Douwe S.

AU - de Vries, Johannes G.

AU - Otten, Edwin

PY - 2018/7/9

Y1 - 2018/7/9

N2 - Water addition to alpha,beta-unsaturated nitriles would give facile access to the -hydroxy-nitriles, which in turn can be hydrogenated to the gamma-amino alcohols. We have previously shown that alcohols readily add in 1,4-fashion to these substrates using Milstein's Ru(PNN) pincer complex as catalyst. However, attempted water addition to alpha,beta-unsaturated nitriles gave the 3-hydroxynitriles in mediocre yields. On the other hand, addition of benzyl alcohol proceeded in excellent yields for a variety of -substituted unsaturated nitriles. Subsequent treatment of the benzyl alcohol addition products with TMSCl/FeCl3 resulted in the formation of 3-hydroxy-alkylnitriles. The 3-benzyloxy-alkylnitriles obtained from oxa-Michael addition also could be hydrogenated directly in the presence of acid to give the amino alcohols as their HCl salts in excellent yields. Hydrogenation under neutral conditions gave a mixture of the secondary and tertiary amines. Hydrogenation in the presence of base and Boc-anhydride gave the orthogonally bis-protected amino alcohols, in which the benzyl ether can subsequently be cleaved to yield Boc-protected amino alcohols. Thus, a variety of molecular scaffolds with a 1,3-relationship between O- and N-functional group is accessible starting from oxa-Michael addition of benzyl alcohol to alpha,beta-unsaturated nitriles.

AB - Water addition to alpha,beta-unsaturated nitriles would give facile access to the -hydroxy-nitriles, which in turn can be hydrogenated to the gamma-amino alcohols. We have previously shown that alcohols readily add in 1,4-fashion to these substrates using Milstein's Ru(PNN) pincer complex as catalyst. However, attempted water addition to alpha,beta-unsaturated nitriles gave the 3-hydroxynitriles in mediocre yields. On the other hand, addition of benzyl alcohol proceeded in excellent yields for a variety of -substituted unsaturated nitriles. Subsequent treatment of the benzyl alcohol addition products with TMSCl/FeCl3 resulted in the formation of 3-hydroxy-alkylnitriles. The 3-benzyloxy-alkylnitriles obtained from oxa-Michael addition also could be hydrogenated directly in the presence of acid to give the amino alcohols as their HCl salts in excellent yields. Hydrogenation under neutral conditions gave a mixture of the secondary and tertiary amines. Hydrogenation in the presence of base and Boc-anhydride gave the orthogonally bis-protected amino alcohols, in which the benzyl ether can subsequently be cleaved to yield Boc-protected amino alcohols. Thus, a variety of molecular scaffolds with a 1,3-relationship between O- and N-functional group is accessible starting from oxa-Michael addition of benzyl alcohol to alpha,beta-unsaturated nitriles.

KW - oxa-Michael addition

KW - amino alcohols

KW - hydrogenation

KW - nitriles

KW - pincer ligand

KW - ruthenium

KW - ENANTIOSELECTIVE BETA-BORYLATION

KW - REDOX-FLOW BATTERY

KW - TRIETHANOLAMINE STEARATE

KW - UNSATURATED NITRILES

KW - CARBOXYLIC-ACIDS

KW - LIGAND

KW - WATER

KW - ACCEPTORS

KW - COMPLEX

KW - HYDROGENATION

U2 - 10.1002/cctc.201800509

DO - 10.1002/cctc.201800509

M3 - Article

VL - 10

SP - 2868

EP - 2872

JO - ChemCatChem

JF - ChemCatChem

SN - 1867-3880

IS - 13

ER -

ID: 64244665