Carbenes electron-deficient

Two Jt-donor a-attractor substituents, that is, a push, push mesomeric-pull, pull inductive substitution pattern. Good examples are diaminocarbenes in which the carbene electron deficiency is reduced by the donation of the two nitrogen lone pairs, while the carbene lone pair is stabilized by the inductive effect of two electronegative nitrogen atoms. 

Reactions with Radicals and Electron-deficient Species Reactions at Surfaces 4.02.1.8.1 Carbenes and nitrenes... 

Electron deficient species can attack the unshared electron pairs of heteroatoms, to form ylides, such as in the reaction of thietane with bis(methoxycarbonyl)carbene. The S —C ylide rearranges to 2,2-bis(methoxycarbonyl)thiolane (Section 5.14.3.10.1). A"-Ethoxycar-bonylazepine, however, is attacked by dichlorocarbene at the C=C double bonds, with formation of the trans tris-homo compound (Section 5.16.3.7). 

The neutral divalent carbon atom of a carbene, CX2, with its six valency electrons is electron deficient and hence electrophilic. The... 

Yet another kind of alkene addition is the reaction of a carbene with an alkene to yield a cyclopropane. A carbene, R2C , is a neutral molecule containing a divalent carbon with only six electrons in its valence shell. It is therefore highly reactive and is generated only as a reaction intermediate, rather than as an isolable molecule. Because they re electron-deficient, carbenes behave as electrophiles and react with nucieophiiic C=C bonds. The reaction occurs in a single step without intermediates. 

The strained bicyclic carbapenem framework of thienamycin is the host of three contiguous stereocenters and several heteroatoms (Scheme 1). Removal of the cysteamine side chain affixed to C-2 furnishes /J-keto ester 2 as a possible precursor. The intermolecular attack upon the keto function in 2 by a suitable thiol nucleophile could result in the formation of the natural product after dehydration of the initial tetrahedral adduct. In a most interesting and productive retrosynthetic maneuver, intermediate 2 could be traced in one step to a-diazo keto ester 4. It is important to recognize that diazo compounds, such as 4, are viable precursors to electron-deficient carbenes. In the synthetic direction, transition metal catalyzed decomposition of diazo keto ester 4 could conceivably furnish electron-deficient carbene 3 the intermediacy of 3 is expected to be brief, for it should readily insert into the proximal N-H bond to... 

The diazo function in compound 4 can be regarded as a latent carbene. Transition metal catalyzed decomposition of a diazo keto ester, such as 4, could conceivably lead to the formation of an electron-deficient carbene (see intermediate 3) which could then insert into the proximal N-H bond. If successful, this attractive transition metal induced ring closure would accomplish the formation of the targeted carbapenem bicyclic nucleus. Support for this idea came from a model study12 in which the Merck group found that rhodi-um(n) acetate is particularly well suited as a catalyst for the carbe-noid-mediated cyclization of a diazo azetidinone closely related to 4. Indeed, when a solution of intermediate 4 in either benzene or toluene is heated to 80 °C in the presence of a catalytic amount of rhodium(n) acetate (substrate catalyst, ca. 1000 1), the processes... 

In the context of 12, the diazo keto function and the thiolactam are in proximity. This circumstance would seem to favor any process leading to the union of these two groupings. It is conceivable that decomposition of the diazo function in 12 with rhodium(n) acetate would furnish a transitory electron-deficient carbene which would be rapidly intercepted by the proximal thiolactam sulfur atom (see 20, Scheme 4). After spontaneous ring contraction of the... 

An ab-initio calculation for (OC)5Cr = Si(OH)H shows parallels to the parent carbon compound. However, the electron deficiency at the silicon atom is significantly higher compared to the carbene complex. The LUMO of the Cr=Si... 

The reactivity of these carbene complexes can be understood as an electron-deficient carbene carbon atom due to the electron-attracting CO groups, while... 

The ability of Fischer carbene complexes to transfer their carbene ligand to an electron-deficient olefin was discovered by Fischer and Dotz in 1970 [5]. Further studies have demonstrated the generality of this thermal process, which occurs between (alkyl)-, (aryl)-, and (alkenyl)(alkoxy)carbene complexes and different electron-withdrawing substituted alkenes [6] (Scheme 1). For certain substrates, a common side reaction in these processes is the insertion of the carbene ligand into an olefinic C-H bond [6, 7]. In addition, it has been ob-... 

Asymmetric versions of the cyclopropanation reaction of electron-deficient olefins using chirally modified Fischer carbene complexes, prepared by exchange of CO ligands with chiral bisphosphites [21a] or phosphines [21b], have been tested. However, the asymmetric inductions are rather modest [21a] or not quantified (only the observation that the cyclopropane is optically active is reported) [21b]. Much better facial selectivities are reached in the cyclopropanation of enantiopure alkenyl oxazolines with aryl- or alkyl-substituted alkoxy-carbene complexes of chromium [22] (Scheme 5). 

Electron-deficient 1,3-dienes are known to react when heated with metho-xy(aryl)- or methoxy(alkyl)carbene complexes to afford vinylcyclopropane derivatives with high regioselectivity and diastereoselectivity [8a, 24]. Cyclo-propanation of the double bond not bearing the acceptor functional group and... 

The diamagnetic ylide complexes 34 have been obtained from the reaction of electron-deficient complexes [MoH(SR)3(PMePh2)] and alkynes (HC=CTol for the scheme), via the formal insertion of the latter into the Mo-P bond. The structural data show that 34 corresponds to two different resonance-stabilized ylides forms 34a (a-vinyl form) and 34b (carbene ylide form) (Scheme 17) [73]. Concerning the group 7 recent examples of cis ylide rhenium complexes 36 cis-Me-Re-Me) have been reported from the reaction of the corresponding trans cationic alkyne derivatives 35 with PR" via a nucleophilic attack of this phosphine at the alkyne carbon. 

These three types, radicals, carbocations and carbanions, by no means exhaust the possibilities of transient intermediates in which carbon is the active centre others include the electron-deficient species carbenes, R2C (p. 266), nitrenes, RN (p. 122) and also arynes (p. 174). 

The rearrangements that we have considered to date all have one feature in common the migration of an alkyl or aryl group, with its electron pair, to a carbon atom which, whether it be a carbocation or not, is electron-deficient. Another atom that can similarly become electron-deficient is nitrogen in, for example, R2N or RN (a nitrene, cf. carbenes above), and it might be expected that alkyl or aryl migration to such centres would take place, just as it did to R3C and R2C this is indeed found to be the case. 

C-NMR chemical shifts are a useful diagnostic tool for carbene complexes, with Ccarb being substantially deshielded. The Ccarb resonance is seen to shift to higher fields as the electron deficiency of the metal center is increased (i.e., with electron-withdrawing ligands and in cationic complexes). 

Fischer carbenes characteristically contain a number of electron-withdrawing carbonyl ligands while the typical Ru, Os, or Ir carbene complexes described above frequently contain several cr-donor ligands. The metal centers in these former compounds, then, are rather electron-deficient, with nucleophilic attack at Ca being a favorable reaction. 

The effect of metal basicity on the mode of reactivity of the metal-carbon bond in carbene complexes toward electrophilic and nucleophilic reagents was emphasized in Section II above. Reactivity studies of alkylidene ligands in d8 and d6 Ru, Os, and Ir complexes reinforce the notion that electrophilic additions to electron-rich compounds and nucleophilic additions to electron-deficient compounds are the expected patterns. Notable exceptions include addition of CO and CNR to the osmium methylene complex 47. These latter reactions can be interpreted in terms of non-innocent participation of the nitrosyl ligand. 

Reactions of 1,3,4-oxadiazoles at the ring atoms with radicals, carbenes, and nitrenes or with other electron-deficient species are rather uncommon. CHEC(1984) and CHEC-II(1996) have reported very few examples of such reactions concerning oxadiazolinones and oxadiazolinethiones. This situation has not changed. 

A more elaborate organochromium method for the generation of 1-substituted isobenzofurans was also reported. As can be seen below, treatment of the o-alkynylbenzaldehyde with the Fischer chromium carbene complex provides the isobenzofuran-Cr(CO)3 complex 128 which can be trapped by the electron-deficient Ai-phenylmaleimide with excellent exo-selectivity. . 

Further work by Trost established the involvement of metallacarbenoid species.292,293 A dimer product 307, incorporating a cyclopropyl group, was observed in the reaction of 304 in the presence of the highly electron-deficient palladole catalyst 305 (Scheme 78). This transformation is the signature of an intermediate of type 306. This chemistry could be rendered useful by playing with other unsaturated bonds as the carbene acceptor, and a variety of polycyclic adducts such as 308 could be synthesized. 

Carbenes ( CR2) and nitrenes ( NR) are short lined reactive intermediates which are electron deficient. They contain a carbon or nitrogen atom with two non-bonding orbitals between which are distributed 2 electrons. These two electrons can be in the same orbital or one electron may be in each. 

Cyloheptatrienylidene carbene is generated when trimethylsilyltropylium tetra-fluonoborate is treated with a stoichiometric excess of tetra-n-butylammonium fluoride in dichloromethane [50], Although the carbene dimerizes readily, it will react with electron-deficient alkenes (see Section 7.3). Tetra-n-butylammonium fluoride in a stoichiometric amount promotes the formation of adamantylidenevinylidene from 2-bromo-2-(trimethylsilylethynyl)adamantane [51 ]. 

Carbenes are electron-deficient two-coordinate carbon compounds that have two nonbonding electrons at one carbon. In the ground state, the two unshared electrons may be either in the same orbital and have antiparallel spins (singlet state S), or in two different orbitals with parallel spins (triplet state T). They can be considered as typical representatives of reactive intermediates and have found a broad range of applications in synthetic chemistry. 

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