2013
DOI: 10.1021/om400565c
|View full text |Cite
|
Sign up to set email alerts
|

Nucleophilic Attack in Methoxycarbenes: Heterolytic Cleavage of the Carbon (sp3)–Oxygen Bond versus Aminolysis

Abstract: The iridium methoxycarbene [IrCp*Cl{C(OMe)-CHCPh 2 }(PPh 2 Me)]PF 6 (3) can undergo a clean attack by nucleophiles at least by two different pathways: (1) an unusual nucleophilic attack of primary, secondary, and tertiary amines at the sp 3 carbon−oxygen bond, which gives an acyl complex and amine alkylation and (2) a nucleophilic attack of the ammonia at the carbenic carbon, which forms a primary aminocarbene.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
3
2

Citation Types

0
10
0

Year Published

2014
2014
2022
2022

Publication Types

Select...
4
1

Relationship

0
5

Authors

Journals

citations
Cited by 14 publications
(10 citation statements)
references
References 34 publications
0
10
0
Order By: Relevance
“…Indirect proof of the conversion of B into C is the formation of the oxacyclocarbene III , which was obtained by intramolecular attack of the hydroxy group at the α carbon [Equation (5)], whereas the formation of the acyl complex D is compatible with the reaction to give product II . The formation of an Ir–carbonyl complex (e.g., II ) via an acyl complex, which we have previously observed,5 is probably linked to the deactivation of the catalyst, which prevents the regeneration of I , thereby lowering the reaction yield, as in the case of the catalytic reaction with 7a . This reaction may be due to the electron‐withdrawing effect of the NO 2 substituent on the phenyl group because when a π donor (OMe) or a weak electron donor (Me) are the substituents on the phenyl group, the Ir–carbonyl complex was not formed.…”
Section: Resultsmentioning
confidence: 69%
See 1 more Smart Citation
“…Indirect proof of the conversion of B into C is the formation of the oxacyclocarbene III , which was obtained by intramolecular attack of the hydroxy group at the α carbon [Equation (5)], whereas the formation of the acyl complex D is compatible with the reaction to give product II . The formation of an Ir–carbonyl complex (e.g., II ) via an acyl complex, which we have previously observed,5 is probably linked to the deactivation of the catalyst, which prevents the regeneration of I , thereby lowering the reaction yield, as in the case of the catalytic reaction with 7a . This reaction may be due to the electron‐withdrawing effect of the NO 2 substituent on the phenyl group because when a π donor (OMe) or a weak electron donor (Me) are the substituents on the phenyl group, the Ir–carbonyl complex was not formed.…”
Section: Resultsmentioning
confidence: 69%
“…We have recently reported on the reactions of [IrCp*Cl(NCMe)(L)][PF 6 ] (L = PMe 3 , PPh 2 Me) with propargylic alcohols 5,6. The (methoxy)alkenylcarbene complexes obtained undergo a cyclometalation reaction to yield iridacycles containing different numbers of atoms 6.…”
Section: Introductionmentioning
confidence: 99%
“…This result agrees with our experimental findings. [11] Undoubtedly, steric hindrance plays a role in this result, since the structures of these transition states are quite compact and the ethylamine molecule is bigger than the ammonia molecule. However, we consider that effects involving the basicity of the nucleophile are also involved.…”
Section: Resultsmentioning
confidence: 99%
“…Nevertheless, in solution more than one molecule of water would likely be in the vicinity of the ammonia molecule, even more likely if we consider that, under the experimental conditions, the percentage of water in the aqueous ammonia solution is 70 %. [11] To reach a more realistic description of the experimental conditions, we studied the two reaction pathways of complex I with ammonia and two water molecules (Figure 8). The energy barrier of the heterolytic cleavage is more than 2 kcal/mol higher than the first barrier of the aminolysis pathway.…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation