2018
DOI: 10.1002/chem.201803506
|View full text |Cite
|
Sign up to set email alerts
|

Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes

Abstract: A novel strategy for the direct enantioselective oxidative homocoupling of α-branched aldehydes is presented. The methodology employs open-shell intermediates for the construction of chiral 1,4-dialdehydes by forming a carbon-carbon bond connecting two quaternary stereogenic centers in good yields and excellent stereoselectivities for electron-rich aromatic aldehydes. The 1,4-dialdehydes were transformed into synthetically valuable chiral pyrrolidines. Experimental mechanistic investigations based on competiti… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
1
1
1

Citation Types

0
21
0

Year Published

2019
2019
2021
2021

Publication Types

Select...
5
2

Relationship

1
6

Authors

Journals

citations
Cited by 35 publications
(21 citation statements)
references
References 45 publications
0
21
0
Order By: Relevance
“…Key empirical observations reveal insights into the reaction mechanism. Single‐electron oxidation processes accountable for previously disclosed couplings were limited to electron‐rich aldehydes whereas the present work also proceeds very well for electron‐poor aldehydes. For example, oxidation of enamines derived from 2‐arylpropanals 1 d – n and isobutyraldehyde 1 p proceeds smoothly in the presence of DDQ and at comparable rates of formation.…”
Section: Resultsmentioning
confidence: 53%
“…Key empirical observations reveal insights into the reaction mechanism. Single‐electron oxidation processes accountable for previously disclosed couplings were limited to electron‐rich aldehydes whereas the present work also proceeds very well for electron‐poor aldehydes. For example, oxidation of enamines derived from 2‐arylpropanals 1 d – n and isobutyraldehyde 1 p proceeds smoothly in the presence of DDQ and at comparable rates of formation.…”
Section: Resultsmentioning
confidence: 53%
“…In contrast, the creation of the structures containing at least one quaternary stereocenter in acyclic systems remains a formidable challenge due to the increased degrees of rotational freedom and steric congestion upon C−C bond formation [5, 6] . Particularly, there is only one example of setting vicinal quaternary carbon stereocenters with both centers in an acyclic chain by Jørgensen through stereoselective oxidative homocoupling of aldehydes [6e, 7, 8] …”
Section: Methodsmentioning
confidence: 99%
“…Very recently, Jørgensen et al . succeeded in developing a direct asymmetric oxidative homocoupling of α‐branched aldehydes with varying yields (28–79%) and enantioselectivities (6–96% ee ) in the presence of 40 mol% chiral amine catalyst and Ag 2 CO 3 as the oxidant (Figure 1c) [10] . Overall, many of the developed methodologies for the stereoselective synthesis of 2,3‐substituted 1,4‐dicarbonyl units achieved sometimes only modest yields and diastereo‐ and/or enantioselectivity.…”
Section: Figurementioning
confidence: 99%