Regioselectivity of the Rhodium‐Catalyzed Hydroboration of Vinyl Arenes: Electronic Twists and Mechanistic Shifts

Edwards, David R.; Hleba, Yonek B; Lata, Christopher J.; Calhoun, Larry A.; Crudden, Cathleen M.

doi:10.1002/anie.200702563

Cited by 61 publications

(23 citation statements)

References 51 publications

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“…No traces of hydrosilylation of the exo-methylene double bond was detected suggesting that the ringopening is again faster that the reductive elimination. [17] When MCPs and ACPs 1 were treated with a slight excess (1.3 equiv) of Bu 3 SnH in THF in the presence of a catalytic amount of [PdA C H T U N G T R E N N U N G (PPh 3 ) 4 ] (3 mol %, method B), [15] the corresponding homoallylstannanes 10 were also obtained in excellent yields as single ringopened products (Table 2, entries [8][9][10][11][12][13][14]. As the ring cleavage preferentially occurs to lead to the primary alkyl metal species 3 in all examined cases (Scheme 2), the integrity of the quaternary stereogenic center should remain unaffected in the process.…”

Section: Communicationmentioning

confidence: 99%

Metal‐Catalyzed Ring‐Opening of Alkylidenecyclopropanes: New Access to Building Blocks with an Acyclic Quaternary Stereogenic Center

Simaan¹,

Goldberg²,

Rosset

et al. 2010

Chemistry A European J

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Open sesame! A selective metal‐catalyzed ring opening of alkylidenecyclopropane derivatives leads to various functionalized acyclic derivatives possessing challenging quaternary stereocenters. The key feature of this transformation is that the ring opening is faster than the reductive elimination and is highly regioselective; a single ring‐opened product was always observed and the stereointegrity of the quaternary stereogenic center remains unaffected in the process.

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Section: Communicationmentioning

confidence: 99%

Metal‐Catalyzed Ring‐Opening of Alkylidenecyclopropanes: New Access to Building Blocks with an Acyclic Quaternary Stereogenic Center

Simaan¹,

Goldberg²,

Rosset

et al. 2010

Chemistry A European J

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“…Hydroboration of styrene: The rhodium-catalyzed hydroboration [29] of styrene with pinacol or catecholborane has been extensively studied with phosphine ligands, [30] but, to our knowledge, only once with NHC ligands.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Electronic Tuning of a Carbene Center via Remote Chemical Induction, and Relevant Effects in Catalysis

César

Lugan

Lavigne

2010

Chemistry A European J

110

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The present report develops the idea that an N-heterocyclic carbene incorporating a remote anionic functionality--here, a malonate group--as a backbone component of its heterocyclic framework, can be "post-functionalized" directly from its transition-metal complexes, upon simple addition of a variety of electrophiles interacting directly with the malonate group in the outer coordination sphere. From a palette of selected electrophilic reagents, it was thus possible to modulate the electronic donor properties of the carbene center over a rather broad range. Both the zwitterionic complex [Rh{malo-NHC}(cod)] and the cationic derivatives [Rh{malo-NHC(E)}(cod)](+) (where "malo-NHC(E)" represents the ligand modified by a selected electrophile "E") were used as pre-catalysts in two types of catalytic reactions, namely, the polymerization of phenylacetylene and the hydroboration of styrene. The results indicate that, in both cases, the zwitterionic species is by far the best catalyst, whereas a decrease in the ligand donicity induced by the added electrophile results in a concomitant reduction of catalytic activity. Apparent deviations to such a trend in the case of the hydroboration of styrene were rationalized in terms of an interaction between the reactive catecholborane substrate and the remote functionality of the N-heterocyclic carbene leading to an in situ modification of the nature of the active species. These observations serve as a useful basis to define the scope and limitations of the present conceptual approach in catalysis.

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“…The catalytic version of this reaction has been most welldeveloped with rhodium catalysts. [47][48][49][50][51][52][53][54][55][56][57][58][59][60] There is very little in the current literature regarding the use of platinum in hydroboration reactions. There is only one example of catechol borane being used in the hydroboration of a terminal alkene with a platinum catalyst.…”

Section: Hydroborationmentioning

confidence: 99%

Synthesis, Structure, and Catalytic Studies of Palladium and Platinum Bis-Sulfoxide Complexes

Drinkel

Linden

et al. 2013

Organometallics

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The bis-sulfoxide ligand p-tolyl-binaso and its derivatives can be used to synthesize neutral and cationic palladium and platinum complexes. Various Pt bis-sulfoxide complexes could be made by using the precursor Pt(M,SS,SS)-p-tolyl-binasoCl2 (5a) and abstracting the chlorides with silver salts. The Pd analogue of this compound (4) could not be used in the same way. In this case, the sulfoxides appear to be very weakly coordinated and different methods to make stable Pd bis-sulfoxide complexes had to be found. The nature of the bonding in the synthesized compounds was studied through analysis of their IR and NMR spectra and X-ray crystal structures. These studies revealed that the trans effect of other ligands in the complex is quite significant in determining the lability of the metal-sulfoxide bond. Some of the more stable platinum structures were then tested for their activity as catalysts in hydroboration and diboration reactions. AbstractThe bissulfoxide ligand, p-tolyl-binaso and its derivatives can be used to synthesize neutral and cationic palladium and platinum complexes. Various Pt bissulfoxide complexes could be made by using the precursor Pt{(M,S S ,S S )-p-tolyl-binaso}Cl 2 (5a) and abstracting the chlorides with silver salts. The Pd analogue of this compound (4) could not be used in the same way. In this case, the sulfoxides appear to be very weakly coordinated and different methods to make stable Pd bissulfoxide complexes had to be found. The nature of the bonding in the synthesized compounds was studied through analysis of their IR and NMR spectra and X-ray crystal structures. These studies revealed that the trans-effect of other ligands in the complex is quite significant in determining the lability of the metal-sulfoxide bond. Some of the more stable platinum structures were then tested for their activity as catalysts in hydroboration and diboration reactions.

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Regioselectivity of the Rhodium‐Catalyzed Hydroboration of Vinyl Arenes: Electronic Twists and Mechanistic Shifts

Cited by 61 publications

References 51 publications

Metal‐Catalyzed Ring‐Opening of Alkylidenecyclopropanes: New Access to Building Blocks with an Acyclic Quaternary Stereogenic Center

Metal‐Catalyzed Ring‐Opening of Alkylidenecyclopropanes: New Access to Building Blocks with an Acyclic Quaternary Stereogenic Center

Electronic Tuning of a Carbene Center via Remote Chemical Induction, and Relevant Effects in Catalysis

Synthesis, Structure, and Catalytic Studies of Palladium and Platinum Bis-Sulfoxide Complexes

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