RuX = C (X  F or H) interactions in complex compounds. Preparation and crystal structures of [) (SC6F5)2(PMe2Ph)2] and [-2)(C6H5)22]

Catalá, Rosa-Maria; Cruz-Garritz, Diana; Sosa, Plinio; Terreros, Pilar; Torrens, Hugo; Hills, Adrian; Hughes, David L.; Richards, Raymond L.

doi:10.1016/0022-328x(89)85432-4

Cited by 52 publications

(22 citation statements)

References 24 publications

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“…The complementary complex 13 produced via h 2 -coordination of the aromatic ring to the metal must experiencea significant back-donation component, because it is most efficiently realized for more electron-deficient aryl rings. Furthermore,f luorophilic interaction [21] could play an important role in stabilization of such complexes with ortho-fluoro-substituted aryl rings.S ubsequents teps, including oxidative addition into BÀHb ond to form Rh III -complex 14,f ollowedb ysyn-specific concertedh ydrorhodationo fc yclopropene andr eductive elimination,a ffords trans-cyclopropyl boronate 5 (Scheme2,C ycle II).…”

Section: Resultsmentioning

confidence: 99%

“…This two-step protocol was employed for preparation of N,N-diethylcycloprop-2-ene-1carboxamides 6a-n,b earing various aryl substituents at C-1 ( Table 2, entries 1-13). Furthermore, employing 1-phenylcycloprop-2-ene-1-carboxylic acid 17 a and different amines 18,w e have synthesized as eries of secondary (6v-y,e ntries [21][22][23][24] and tertiarya mides 6o-t (entries [14][15][16][17][18][19], including Weinreb amide 6u (entry 20). [22] To test the efficiency of cyclopropene carboxamides in the directeda symmetrich ydroboration, we subjected compound 6a to standardr eactionc onditions with pinacolboranei nt he presenceo f[ Rh(COD)Cl] 2 (3 mol %) and chiral diphosphine ligand (6 mol %).…”

Section: Resultsmentioning

confidence: 99%

“…Finally,W einreb amide 6u,a menable for subsequent func-tionalization, [7a, 26] reacted smoothly to provide cis-boronate 7u (entry 20). Hydroboration of secondary amides bearing either a primary (6v)o rasecondary (6w)a lkyl group at nitrogen atom provedv ery efficient and highly selective (entries [21][22]. N-(Furan-2-ylmethyl)-substituted analogue 7x was also obtained very selectively,a lthough chemical yield in this reaction was ratherp oor (entry 22).…”

Section: Resultsmentioning

confidence: 99%

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Directed Rh^I‐Catalyzed Asymmetric Hydroboration of Prochiral 1‐Arylcycloprop‐2‐Ene‐1‐Carboxylic Acid Derivatives

Edwards

Rubina

Rubin

2017

Chemistry A European J

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A full account on rhodium-catalyzed asymmetric, directed hydroboration of functionalized prochiral cyclopropenes affording enantiomerically enriched cyclopropylboronates is reported. The scope and limitations of two alternate directing groups, ester and carboxamide, are evaluated. It was found that hydroboration of esters appeared to be more sensitive to substitution in the aromatic ring of the substrates. Specifically, ortho-halogens were detrimental for diastereo- and enantioselectivity, possibly because of additional coordination with rhodium. In contrast, more Lewis-basic amide directing groups allowed for stronger chelation to the transition metal, leading to consistently high diastereo- and enantioselectivity in hydroboration across a broader range of substrates.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Directed Rh^I‐Catalyzed Asymmetric Hydroboration of Prochiral 1‐Arylcycloprop‐2‐Ene‐1‐Carboxylic Acid Derivatives

Edwards

Rubina

Rubin

2017

Chemistry A European J

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“…Reports of intermolecular C-F bond activation have appeared from no fewer than eight laboratories since that time (184,185). It is interesting to note that there are also several structural reports of transition metal complexes with agostic C-F interactions (186)(187)(188). While most of the reports of C-F bond activation involve unsaturated or aromatic fluorocarbons, the most recent reports from the laboratories of Andersen (184) and Richmond (185) also involve saturated fluorocarbons.…”

Section: C-f Bond Activationmentioning

confidence: 91%

Inorganic Fluorine Chemistry

Thrasher

Strauss

1994

ACS Symposium Series

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Fluorine and fluorinated substituent groups play an increasingly important role in modern inorganic chemistry. Many advances in solid-sate chemistry, coordination chemistry, main group element chemistry, and organometallic chemistry rely on the unique physical and chemical properties of the most electronegative of the chemical elements. This chapter lists the important monographs and reviews that have been published during the last twenty-five years in this area as well as some thoughts about where the field of inorganic fluorine chemistry is heading.The unusual properties exhibited by numerous materials upon the incorporation of either fluorine or fluorine-containing substituents are no longer just topics of idle curiosity for the academician, but are the driving force behind developments in the field of fluorine chemistry. Many advances have either recently found or await commercialization as witnessed by the increasing diversity of industrial applications of fluorine compounds (7-7). Two illustrative examples of the current importance of inorganic fluorine chemistry to industry are the development of both chlorofluorocarbon (CFC) alternatives and new precursors for chemical vapor deposition (CVD) of inorganic materials. Although the CFC alternatives will almost certainly be organofluorine compounds, the processes being developed to produce these materials cannot escape the use of inorganic fluorine chemistry in terms of catalysts (8-15), halogen exchange reagents (16-20), and the like. The references given here serve only as representative examples; the current patent literature is full of references in light of the global concern to help halt the depletion of stratospheric ozone. The second aforementioned case falls into the increasingly important area of materials science. For example, a number of groups have recently taken advantage of the well-known increase in volatility associated with fluorine incorporation to make a series of volatile metal alkoxides which serve as new precursors for CVD of metal fluorides (21-28). Separate chapters on both of these topics of industrial importance appear later in this book.

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“…) and some 0.2 Å longer than in tetra-coordinate [Ru II (SC 6 F 5 ) 2 (PPh 3 ) 2 ] (Catalá et al, 1987(Catalá et al, , 1989. There is no elongation of the C2-H2 bond in (I) as observed in the P2 1 /n modification of [RuCl 2 (PPh 3 ) 3 ], so overall there appears to be no strong C2-H2Á Á ÁRu1 interaction in (I).…”

mentioning

confidence: 93%

Dichlorotris(triphenylphosphine)ruthenium(II) dichloromethane hemisolvate

Cowley

Dilworth

2005

Acta Cryst E

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A third modification of [RuCl2(PPh3)3] has been characterized, this time as the title compound, [RuCl2(C18H15P)3]·0.5CH2Cl2. As seen for the previous modifications, the complex has a distorted square‐pyramidal geometry with an ortho‐H atom `blocking' the site trans to the apical PPh3 ligand. There is no evidence for a strong C—H⋯Ru interaction nor any specific directional force in the solid state.

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RuX = C (X  F or H) interactions in complex compounds. Preparation and crystal structures of [) (SC6F5)2(PMe2Ph)2] and [-2)(C6H5)22]

Cited by 52 publications

References 24 publications

Directed Rh^I‐Catalyzed Asymmetric Hydroboration of Prochiral 1‐Arylcycloprop‐2‐Ene‐1‐Carboxylic Acid Derivatives

Directed Rh^I‐Catalyzed Asymmetric Hydroboration of Prochiral 1‐Arylcycloprop‐2‐Ene‐1‐Carboxylic Acid Derivatives

Inorganic Fluorine Chemistry

Dichlorotris(triphenylphosphine)ruthenium(II) dichloromethane hemisolvate

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RuX = C (X  F or H) interactions in complex compounds. Preparation and crystal structures of [) (SC6F5)2(PMe2Ph)2] and [-2)(C6H5)22]

Cited by 52 publications

References 24 publications

Directed RhI‐Catalyzed Asymmetric Hydroboration of Prochiral 1‐Arylcycloprop‐2‐Ene‐1‐Carboxylic Acid Derivatives

Directed RhI‐Catalyzed Asymmetric Hydroboration of Prochiral 1‐Arylcycloprop‐2‐Ene‐1‐Carboxylic Acid Derivatives

Inorganic Fluorine Chemistry

Dichlorotris(triphenylphosphine)ruthenium(II) dichloromethane hemisolvate

Contact Info

Product

Resources

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Directed Rh^I‐Catalyzed Asymmetric Hydroboration of Prochiral 1‐Arylcycloprop‐2‐Ene‐1‐Carboxylic Acid Derivatives

Directed Rh^I‐Catalyzed Asymmetric Hydroboration of Prochiral 1‐Arylcycloprop‐2‐Ene‐1‐Carboxylic Acid Derivatives