+ Site Statistics
References:
54,258,434
Abstracts:
29,560,870
PMIDs:
28,072,757
+ Search Articles
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ PDF Full Text
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Translate
+ Recently Requested

Rhodium-Catalyzed Alkene Difunctionalization with Nitrenes



Rhodium-Catalyzed Alkene Difunctionalization with Nitrenes



Chemistry 22(27): 9338-9347



The Rh(II) -catalyzed oxyamination and diamination of alkenes generate 1,2-amino alcohols and 1,2-diamines, respectively, in good to excellent yields and with complete regiocontrol. In the case of diamination, the intramolecular reaction provides an efficient method for the preparation of pyrrolidines, and the intermolecular reaction produces vicinal amines with orthogonal protecting groups. These alkene difunctionalizations proceed by aziridination followed by nucleophilic ring opening induced by an Rh-bound nitrene generated in situ, details of which were uncovered by both experimental and theoretical studies. In particular, DFT calculations show that the nitrogen atom of the putative [Rh]2 =NR metallanitrene intermediate is electrophilic and support an aziridine activation pathway by N⋅⋅⋅N=[Rh]2 bond formation, in addition to the N⋅⋅⋅[Rh]2 =NR coordination mode.

(PDF emailed within 0-6 h: $19.90)

Accession: 058773548

Download citation: RISBibTeXText

PMID: 27258005

DOI: 10.1002/chem.201600393


Related references

Mechanistic approaches to palladium-catalyzed alkene difunctionalization reactions. Organic & Biomolecular Chemistry 6(22): 4083-4088, 2008

Use of aryl chlorides as electrophiles in Pd-catalyzed alkene difunctionalization reactions. Journal of Organic Chemistry 75(8): 2756-2759, 2010

Advancing the mechanistic understanding of an enantioselective palladium-catalyzed alkene difunctionalization reaction. Journal of the American Chemical Society 132(49): 17471-17482, 2013

N-tosyloxycarbamates as a source of metal nitrenes: rhodium-catalyzed C-H insertion and aziridination reactions. Journal of the American Chemical Society 127(41): 14198-9, 2005

Merging C-H activation and alkene difunctionalization at room temperature: a palladium-catalyzed divergent synthesis of indoles and indolines. Organic Letters 17(3): 672-675, 2015

Synthesis and preliminary biological studies of 3-substituted indoles accessed by a palladium-catalyzed enantioselective alkene difunctionalization reaction. Journal of the American Chemical Society 132(23): 7870-7871, 2010

Oxidant-free rhodium(I)-catalyzed difunctionalization of acrylamide: an efficient approach to synthesize oxindoles. Organic Letters 17(9): 2142-2145, 2015

Rhodium N-confused porphyrin-catalyzed alkene cyclopropanation. Chemical Communications: 4335-4337, 2006

Effect of triarylphosphane ligands on the rhodium-catalyzed hydrosilylation of alkene. Applied Organometallic Chemistry 28(2): 120-126, 2014

Rhodium-Catalyzed Stereoselective Intramolecular [5 + 2] Cycloaddition of 3-Acyloxy 1,4-Enyne and Alkene. Organic Letters 17(20): 5128-5131, 2016

Traceless chelation-controlled rhodium-catalyzed intermolecular alkene and alkyne hydroacylation. Chemistry 19(9): 3125-3130, 2013

Rhodium-catalyzed linear cross-trimerization of two different alkynes with an alkene and two different alkenes with an alkyne. Chemistry 18(30): 9225-9229, 2012

Rhodium(III)-catalyzed arene and alkene C-H bond functionalization leading to indoles and pyrroles. Journal of the American Chemical Society 132(51): 18326-18339, 2011

Rhodium(I)-catalyzed cycloisomerization of alkene-substituted allenylcyclopropanes: stereoselective formation of bicyclo[4.3.0]nonadienes. Angewandte Chemie 52(43): 11369-11372, 2013

Rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes through C(sp²)-H/alkene functionalization. Angewandte Chemie 53(42): 11338-11341, 2015