Preparation and Wittig reactivity of organotransition-metal-substituted phosphonium salts

Lee, Si Geun; Chung, Young Keun; Yoon, Tae Sung; Shin, Wonjae

doi:10.1021/om00032a001

Cited by 12 publications

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“…They include imine, cyano, sulfonyl, nitro, and alkoxycarbonyl [143,144] as well as more esoteric substituents such as diazo [145], phosphine [146], phosphate [147], metal carbene [148], and Cr(CO) 3 [149,150]. Malonate, on the other hand, adds but the resulting carbon-arene bond is too weak and is cleaved under demetallation conditions to regenerate the starting material [151].…”

Section: Addition/oxidation With Arene-mn(co) 3 Cation Complexesmentioning

confidence: 99%

(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

Semmelhack

Chlenov

2004

Topics in Organometallic Chemistry

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Transition metals coordinated to the pi system of arenes function as strong electronwithdrawing groups and favor nucleophilic addition to the arene to give cyclohexadienyl-metal complexes. The regioselectivity of addition is influenced in subtle and indirect ways, compared to the powerful effect on both reactivity and regioselectivity of electron-withdrawing groups attached to the sigma bond system of the arene. The intermediate cyclohexadienyl complexes can be processed in several ways, leading to several distinct synthesis methods. Useful reactivity is known for several metal systems and each is discussed for specific reaction types. The presence of a fluoro or chloro substituent on the arene allows an effective analog of classical S N Ar reactivity, with a wide range of nucleophiles including simple amines, alkoxides, and carbon anions. Another general process is the addition/protonation protocol, where a hydrogen substituent on the arene is replaced by a nucleophile. This opens new questions of regioselectivity since the typical arene ligand has several hydrogens which are candidates for substitution. The formation of five-and six-membered rings by both general mechanisms are known. Less general indirect mechanisms (e.g., tele substitution) have also been defined.

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Section: Addition/oxidation With Arene-mn(co) 3 Cation Complexesmentioning

confidence: 99%

(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

Semmelhack

Chlenov

2004

Topics in Organometallic Chemistry

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“…Noteworthy additions to this list include trialkylaluminum reagents, 3 a-iminoester, a-iminonitrile, a-sulfonyl, and a-nitro carbanions, 4 a-haloester carbanions and nitrile anions, 5 sodium cyclopentadienide, 6 a-diazo anion, 7 and Wittig reagents. 8 Use of a Wittig reagent presents the opportunity for further transformation of the resulting (T| 5 -cyclohexadienyl)manganese complex (3), as deprotonation of complex (3) followed by reaction with aldehydes generates the expected alkene (4), mainly as the cis stereoisomer (Equation (2)). 8 Reaction of cation (1) with the tetracarbonylosmium dianion provides the bis[(t| 5 -cyclohexadienyl)manganese]tetracarbonylosmium complex (5), a rare example o f the reaction of a transition metal nucleophile with a transition metal 7i-complex (Equation (3)).…”

Section: (V-arene)manganese Complexesmentioning

confidence: 99%

“…8 Use of a Wittig reagent presents the opportunity for further transformation of the resulting (T| 5 -cyclohexadienyl)manganese complex (3), as deprotonation of complex (3) followed by reaction with aldehydes generates the expected alkene (4), mainly as the cis stereoisomer (Equation (2)). 8 Reaction of cation (1) with the tetracarbonylosmium dianion provides the bis[(t| 5 -cyclohexadienyl)manganese]tetracarbonylosmium complex (5), a rare example o f the reaction of a transition metal nucleophile with a transition metal 7i-complex (Equation (3)). 9 Substitution of a carbon monoxide ligand by phosphites has also been reported, and electrocatalytic carbon monoxide substitution by phosphites is chemically irreversible up to a range of 20 V s .°N …”

Section: (V-arene)manganese Complexesmentioning

confidence: 99%

“…Although attack of the nucleophile takes place almost exclusively exo to the metal, tricarbonyl-(r| 5 -cyclohexadienyl)manganese complex (8), the result of endo hydride attack, has been reported to predominate when bulky hydrides and protic solvents are utilized with the more sterically demanding (hexamethyl-t| 6 -benzene)manganese complex (6) (Equation (4)). 11 Reaction of tricarbonyl-(t| 6 -benzene)manganese cation (1) with PhSLi also gives rise to endo-substituted (T^5-cyclohexadienyl)-manganese complexes, apparently via initial attack at a carbonyl ligand followed by migration to the arene.…”

Section: (5)mentioning

confidence: 99%

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Manganese Hydrocarbon Complexes Excluding Cyclopentadienyl

McDaniel

1995

Comprehensive Organometallic Chemistry II

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Cationic (η⁶‐arene)‐ and Neutral (η⁵‐cyclohexadienyl)‐tricarbonylmanganese Complexes: Synthesis and Reactivity

Rose‐Munch

Rose

Eloi

2010

Patai's Chemistry of Functional Groups

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The tricarbonyl‐chromium and ‐manganese groups are known to easily coordinate arene rings to form η 6 ‐arene complexes. The electrophilic nature of the tricarbonyl metal fragments makes the arene electron‐deficient and renders it susceptible to nucleophilic attack. It is for these reasons that a new trend has emerged, the study of the chemistry of (η 5 ‐cyclohexadienyl)Mn(CO) 3 complexes which are easily obtained by addition of a nucleophile to the arene ring. In the last ten years, the discovery of new methods of functionalization involving Pd cross‐coupling and lithiation reactions has greatly expanded the scope of the (η 5 ‐cyclohexadienyl)Mn(CO) 3 complexes and consequently represents a key step in the development of the arene manganese chemistry since [(η 6 ‐arene)Mn(CO) 3 ] + complexes can be easily obtained by rearomatization of the corresponding (η 5 ‐cyclohexadienyl)Mn derivatives. The present review aims to describe the situation for the synthesis and the reactivity of η 6 ‐arene‐Mn complexes as well as that of η 5 ‐cyclohexadienyl‐Mn complexes to highlight the recent breakthrough in their chemistry. The main reactivities described for η 5 Mn complexes correspond to nucleophilic addition, lithiation/electrophilic quench, lithium/halogen exchange and Pd catalyzed reactions. These types of reactions can be efficiently compared with those well studied in η 6 arenetricarbonylchromium complexes. All these recent developments in the functionalization of η 5 ‐ and η 6 ‐Mn complexes described in this chapter clearly open a revival period for this type of complexes which are starting to emerge as a valuable and versatile class of compounds more environmentally friendly than their Cr analogs.

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Preparation and Wittig reactivity of organotransition-metal-substituted phosphonium salts

Cited by 12 publications

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(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

Manganese Hydrocarbon Complexes Excluding Cyclopentadienyl

Cationic (η⁶‐arene)‐ and Neutral (η⁵‐cyclohexadienyl)‐tricarbonylmanganese Complexes: Synthesis and Reactivity

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Preparation and Wittig reactivity of organotransition-metal-substituted phosphonium salts

Cited by 12 publications

References 0 publications

(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

Manganese Hydrocarbon Complexes Excluding Cyclopentadienyl

Cationic (η6‐arene)‐ and Neutral (η5‐cyclohexadienyl)‐tricarbonylmanganese Complexes: Synthesis and Reactivity

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Cationic (η⁶‐arene)‐ and Neutral (η⁵‐cyclohexadienyl)‐tricarbonylmanganese Complexes: Synthesis and Reactivity