Asymmetric synthesis of homoallylic amines bearing adjacent stereogenic centers by addition of substituted allylic zinc reagents to N-tert-butanesulfinylimines.

Org Lett

Chemical and Analytical Development, Novartis Pharmaceuticals Corporation, East Hanover, New Jersey 07936, USA.

Published: July 2008

A highly diastereoselective addition of substituted racemic allylic zinc reagents to chiral N- tert-butanesulfinylimines resulting in the formation of homoallylic amines is reported. This method is quite general and also efficient for the preparation of enantiomerically pure homoallylic amines bearing quaternary centers and also adjacent quaternary centers.

Download full-text PDF

Source
http://dx.doi.org/10.1021/ol800998uDOI Listing

Publication Analysis

Top Keywords

homoallylic amines
12
amines bearing
8
addition substituted
8
allylic zinc
8
zinc reagents
8
quaternary centers
8
asymmetric synthesis
4
synthesis homoallylic
4
bearing adjacent
4
adjacent stereogenic
4

Similar Publications

Reactivity of Anomalous Aziridines for Versatile Access to High Fsp Amine Chemical Space.

Acc Chem Res

January 2025

Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, United States.

ConspectusThe manipulation of strained rings is a powerful strategy for accessing the valuable chemical frameworks present in natural products and active pharmaceutical ingredients. Aziridines, the smallest N-containing heterocycles, have long served as building blocks for constructing more complex amine-containing scaffolds. Traditionally, the reactivity of typical aziridines has been focused on ring-opening by nucleophiles or the formation of 1,3-dipoles.

View Article and Find Full Text PDF

A straightforward and highly diastereoselective synthesis of -4-hydroxypiperidines is presented. This method allows access to C2 and C4 substituted piperidines, bearing a tetrasubstituted carbon stereocenter at C4. -Disubstituted homoallylic amines and ketoaldehydes as carbonyl partners have been rarely used in aza-Prins cyclizations, expanding the scope of this reaction.

View Article and Find Full Text PDF

Using amines in catalytic transfer hydrogenation (TH) is challenging, despite their potential availability as a hydrogen source. Here, we describe a photoredox/nickel-catalyzed TH of alkyne through an intermediary aminoalkyl Ni species. This reaction successfully provided functionalized ()-alkenes, such as (homo)allyl ethers, alcohols, and amides (/ = up to >99:1), and the reaction thus bypasses a limitation of substrate scope in TH using amine and a Lindlar catalyst.

View Article and Find Full Text PDF

Asymmetric organocatalytic synthesis of chiral homoallylic amines.

Beilstein J Org Chem

September 2024

Department of Chemistry, Loughborough University, Loughborough, LE11 3TU, UK.

In recent decades, the chiral allylation of imines emerged as a key methodology in the synthesis of alkaloids and natural products with 4-, 5- and 6-membered cyclic amine motifs. Initially reliant on stoichiometric reagents, synthetic chemists predominantly used -substituted chiral imines, organometallic chiral reagents and achiral reagents with an equimolar chiral controller. However, recent years have witnessed the rise of asymmetric transition-metal catalysts and, importantly, organocatalytic allylation, reshaping the landscape of modern synthetic chemistry.

View Article and Find Full Text PDF

The unexpected 4,1-hydroaminoalkylation of dienes provides selective access to linear homoallylic amines by zirconium catalysis. This switch from the traditional branched preferred regioselectivity to selective linear product formation using this early transition metal can be attributed to π-allyl intermediates. The reactivity of these isolated intermediates on a sterically accessible and coordinatively flexible chelating bis(ureate) Zr(iv) complex confirmed reversible C-C bond formation in hydroaminoalkylation catalysis.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!