2022
DOI: 10.1002/ange.202113827
|View full text |Cite
|
Sign up to set email alerts
|

Hydrogenative Cycloisomerization and Sigmatropic Rearrangement Reactions of Cationic Ruthenium Carbenes Formed by Catalytic Alkyne gem‐Hydrogenation

Abstract: gem‐Hydrogenation of propargyl alcohol derivatives with [CpXRu(MeCN)3]PF6 (CpX=substituted cyclopentadienyl) as catalysts affords cationic pianostool ruthenium carbene complexes which are so electrophilic that they attack a tethered olefin to furnish cyclopentene products; cyclopropanation or metathesis do not compete with this novel transformation. If the transient carbenes carry appropriate propargylic substituents, however, they engage in ([2,3]‐sigmatropic) rearrangements to give enol esters (carbonates, c… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1

Citation Types

0
3
0

Year Published

2022
2022
2022
2022

Publication Types

Select...
7

Relationship

1
6

Authors

Journals

citations
Cited by 7 publications
(3 citation statements)
references
References 65 publications
(35 reference statements)
0
3
0
Order By: Relevance
“…5a). 105,106,108 While the production of hyperpolarised CH 2 groups via geminal PHIP is possible (Fig. 5b), a challenge of this approach is the slower reaction times compared to traditional PHIP.…”
Section: Ruthenium Catalysts For Trans and Geminal Alkene Hydrogenationsmentioning
confidence: 99%
“…5a). 105,106,108 While the production of hyperpolarised CH 2 groups via geminal PHIP is possible (Fig. 5b), a challenge of this approach is the slower reaction times compared to traditional PHIP.…”
Section: Ruthenium Catalysts For Trans and Geminal Alkene Hydrogenationsmentioning
confidence: 99%
“…In carbene chemistry, transition-metal catalysts with periodic table group 8–11 elements are commonly employed as a catalytic core to generate metal–carbene species from corresponding diazo compounds or their related precursors (Figure a). Metal-carbene reactions using unique catalyst platforms with Rh, , Cu, , Pd, , Ir, Ru, , Co, Au , etc., to achieve carbon homologation have been tremendously successful . To reduce the environmental load, the development of transition-metal free reactions using various conditions and reagents, such as blue light, Brønsted acid, organic silanes, and organoboranes, has gained momentum.…”
Section: Introductionmentioning
confidence: 99%
“…shift 1 to the corresponding (E)-alkene as the final product; gem-hydrogenation 2 is hence innately linked to alkyne trans-hydrogenation, [1,7] which itself is a rather unorthodox but synthetically enabling transformation. [5,6,8,9] Importantly, however, it is also possible to outperform this downstream pathway and, in doing so, harness genuine carbene reactivity: a set of previously unknown transformations, including hydrogenative cyclopropanation, [10] hydrogenative metathesis, [10,11] hydrogenative rearrangement and cycloisomerization reactions, [12,13] hydrogenative heterocycle syntheses, [14] and hydrogenative CÀ H insertions [15] bear witness of this notion.…”
Section: Introductionmentioning
confidence: 99%