Synlett 2021; 32(05): 472-487
DOI: 10.1055/a-1308-0021
account
The Power of Transition Metals: An Unending Well-Spring of New Reactivity

Palladium-Catalyzed Functionalization of Olefins and Alkynes: From Oxyalkynylation to Tethered Dynamic Kinetic Asymmetric Transformations (DYKAT)

Stefano Nicolai
,
Ugo Orcel
,
Bastian Muriel
,
Phillip D. G. Greenwood
,
Luca Buzzetti
,
Mikus Puriņš
,
Jerome Waser
We thank the Swiss National Science Foundation (Grants 20021_119810 and 20021_15992), ERC (European Research Council, Starting Grant iTools4MC, number 334840 and Consolidator Grant, SeleCHEM, number 771170), and EPFL for financial support.


Abstract

This review presents an account of the palladium-catalyzed functionalizations of alkenes and alkynes developed at the Laboratory of Catalysis and Organic Synthesis (LCSO). Starting from the intramolecular oxy- and aminoalkynylation of alkenes, tethered methods were then developed to functionalize allylic amines and alcohols, as well as propargylic amines. Finally, a new dynamic kinetic asymmetric transformation was developed based on the use of a ‘one-arm’ Trost-type ligand, giving access to enantiopure amino alcohols. Each section is a personal account by the researcher(s) who performed the work.

1 Introduction,

2 Oxy- and Aminoalkynylation of Olefins,

3 In Situ Tethering Strategies for the Synthesis of Vicinal Amino Alcohols and Diamines,

4 Carboamination of Allylic Alcohols,

5 Carbooxygenation of Propargylic Amines,

6 Enantioselective Carboetherification/Hydrogenation via a Catalytically Formed Chiral Auxiliary,

7 Conclusion



Publication History

Received: 30 October 2020

Accepted after revision: 10 November 2020

Accepted Manuscript online:
10 November 2020

Article published online:
10 December 2020

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