Reductive Amination Revisited: Reduction of Aldimines with Trichlorosilane Catalyzed by Dimethylformamide─Functional Group Tolerance, Scope, and Limitations

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F22%3A00552367" target="_blank" >RIV/61388963:_____/22:00552367 - isvavai.cz</a>

Alternative codes found

RIV/00216208:11160/22:10450571 RIV/00216208:11310/22:10450571

Result on the web

<a href="https://doi.org/10.1021/acs.joc.1c01561" target="_blank" >https://doi.org/10.1021/acs.joc.1c01561</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.joc.1c01561" target="_blank" >10.1021/acs.joc.1c01561</a>

Result language

angličtina

Original language name

Reductive Amination Revisited: Reduction of Aldimines with Trichlorosilane Catalyzed by Dimethylformamide─Functional Group Tolerance, Scope, and Limitations

Original language description

Aldimines, generated in situ from aliphatic, aromatic, and heteroaromatic aldehydes and aliphatic, aromatic, and heteroaromatic primary or secondary amines, can be reduced with trichlorosilane in the presence of dimethylformamide (DMF) as an organocatalyst (≤10 mol %) in toluene or CH2Cl2 at room temperature. The reduction tolerates ketone carbonyls, esters, amides, nitriles, sulfones, sulfonamides, NO2, SF5, and CF3 groups, boronic esters, azides, phosphine oxides, C═C and C≡C bonds, and ferrocenyl nucleus, but sulfoxides and N-oxides are reduced. α,β-Unsaturated aldimines undergo 1,2-reduction only, leaving the C═C bond intact. N-Monoalkylation of primary amines is attained with a 1:1 aldehyde to amine ratio, whereas excess of the aldehyde (≥2:1) allows second alkylation, giving rise to tertiary amines. Reductive N-alkylation of α-amino acids proceeds without racemization, the resulting products, containing a C≡C bond or N3 group, are suitable for click chemistry. This reaction thus offers advantages over the traditional methods (borohydride reduction or catalytic hydrogenation) in terms of efficiency and chemoselectivity. Solubility of some of the reacting partners appears to be the only limitation. The byproducts generated by the workup with aqueous NaHCO3 (i.e., NaCl and silica) are environmentally benign. As a greener alternative, DMA can be employed as a catalyst instead of DMF.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10401 - Organic chemistry

Project

<a href="/en/project/EF16_019%2F0000841" target="_blank" >EF16_019/0000841: Efficiency and safety improvement of current drugs and nutraceuticals: advanced methods - new challenges</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2022

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Organic Chemistry

ISSN

0022-3263

e-ISSN

1520-6904

Volume of the periodical

87

Issue of the periodical within the volume

2

Country of publishing house

US - UNITED STATES

Number of pages

24

Pages from-to

920-943

UT code for WoS article

000745225300001

EID of the result in the Scopus database

2-s2.0-85123289060