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Cyclic alkyl

Nitro compounds have been converted into various cyclic compounds via cycloaddidon reactions. In particular, nitroalkenes have proved to be nsefid in Diels-Alder reactions. Under thermal conditions, they behave as electron-deficient alkenes ind react v/ith dienes to yield 3-nitrocy-clohexenes. Nitroalkenes c in also act as heterodienes ind react v/ith olefins in the presence of Lewis acids to yield cyclic alkyl nkronates, which undergo [3- 2 cycloaddidon. Nitro compounds are precursors for nitnie oxides, alkyl nitronates, and trialkylsilyl nitronates, which undergo [3- 2 cycloaddldon reacdons. Thus, nitro compounds play important roles in the chemistry of cycloaddidon reacdons. In this chapter, recent developments of cycloaddinon chemistry of nitro compotmds and their derivadves are summarized. [Pg.231]

Fig. 3.18 Catalysts 46-48 bearing cyclic (alkyl)(amino)carbenes... Fig. 3.18 Catalysts 46-48 bearing cyclic (alkyl)(amino)carbenes...
DIAZOCYCLOHEXANONE, 51, 86 a-Diazoketones, reaction with trialkylborane, 53, 82 rearrangement, 52, 53 synthesis, 52, 53 >°-Diazoketones, aromatic, from acid chlorides, 53, 37 -Diazoketones, cyclic, alkylation of, 53, 82, 83 Diazomethane, in modified Arndt-... [Pg.128]

Table 3 Radical stabilization energies (in kj/mol) of cyclic alkyl radicals at 0 K according to Eq. 1 ... Table 3 Radical stabilization energies (in kj/mol) of cyclic alkyl radicals at 0 K according to Eq. 1 ...
With mercury(II) nitrate, the five-membered ring peroxide was obtained as an approximately equimolar mixture of isomers, while the 1,2-dioxacyclohexane contained about three times as much trans- as ds-isomer. Peroxymercuration of alkyl-substituted 1,4-penta- and 1,5-hexadienes, followed by demercuration, afforded mixtures of isomeric cyclic alkyl peroxides in yields strongly dependent on the number and position of the substituents175. [Pg.637]

Reductive ring opening of cyclic -alkyl andinium salts happens regioselectively at the Al-aryl bond to form an N, -dialkyl amine. A 2e reduction has been proposed, followed by cleavage to the most stable carbanion (Fig. 23) [122]. [Pg.414]

In addition to complexes of type 44 with a C2 coordinated NHC ligand, complexes of type 45 with abnormal C4 or C5 bound carbene ligands have recently been described (Fig. 16) [143, 144]. The carbene carbon atom in these complexes is stabilized by only one nitrogen atom. A similar situation has been observed for the cyclic (alkyl)(amino)carbene (type 16, Fig. 6) [38, 39]. [Pg.111]

The cyclic version of alkylaminocarbenes, the cyclic alkyl aminocarbenes 10c (CAACs), have also been reported [36]. The rigid cyclic structure with very bulky substituents at the nitrogen atom increases the S/T energy gap (45.1 kcal/mol) [37]. Due to this electronic effect as well as to the more resistant substituent pattern, CAACs are much more resistant than the acyclic ones. [Pg.135]

Tris(ligand) complexes involving ligand (41), or derivatives thereof, have been synthesized and characterized. Appending electron-releasing Ph or cyclic alkyl groups to the ligand leads to a blue... [Pg.581]

AUcoxy groups or halogen atoms at the a- or -position of open-chain or cyclic alkyl-lithiums diminish the basicity of such species and hence facilitate the halogen/metal permutation. Other than fert-butyllithium, also iec-butyUithium or butyllithium, even methyllithium, or phenyllithium, can now be employed (Tables 10 and 11). [Pg.441]

Nitronates have also been applied in intramolecular 1,3-dipolar cycloaddition reactions. Denmark and Thorarensen (64) extensively studied the application of cyclic alkyl nitronates in tandem[4+2]/[3+2] cycloadditions of nitroalkanes. In most cases, the stereoselectivity of these reactions is directed by a chiral auxiliary and will thus be outlined in Section 12.3.4. The reader is also directed to the excellent chapter by Denmark in Chapter 2. [Pg.848]

Cyclic alkyl nitronates may be used in tandem [4+2]/[3+2] cycloadditions of nitroalkanes, and this reaction has been extensively studied by Denmark et al. (64,333-335). In recent work, they developed the silicon-tethered heterodiene-alkene 219 (Scheme 12.63). Steric hindrance and the fact that both the nitroalkene and the a,p-unsaturated ester in 219 are electron deficient renders the possibility of self-condensation. Instead, 219 reacts with the electron-rich chiral vinyl ether 220 in the presence of the catalyst 224 to form the intermediate chiral nitronate 221. The tandem reaction proceeds from 221 with an intramolecular 1,3-dipolar cycloaddition to form 222 with 93% de. Further synthetic steps led to the formation of ( )-detoxinine 223 (333). A similar type of tandem reaction has also been applied by Chattopadhyaya and co-workers (336), using 2, 3 -dideoxy-3 -nitro-2, 3 -didehydrothymidine as the starting material (336). [Pg.863]

Methylation is taken as illustrative of alkylation for comparative purposes in Table 25 however, a wide range of other alkylations have been studied (76MI20503). Photolysis of di-r-butyl peroxide in a mixture of cyclohexane and pyridine gives cyclohexylation (equation 170) (7lCR(C)(272)854>. The relative rates for homolytic substitution of pyridines by cyclic alkyl radicals have been obtained (74JCS(P2)1699). A striking contrast can be seen (Table 26)... [Pg.296]

The reactions of chiral cyclic alkyl nitronates have been described (62-64). These nitronates are intermediates in a tandem[4+2]/[3+2] cycloadditions. [Pg.674]

Answer 111-i is a cyclic alkyl bromide (I-broiiio-2-mcNiy -cyciohexane). [Pg.40]

Stable cyclic (alkyl)(amino)carbenes (CAAC) have been developed by Bertrand et al. and can be readily prepared in a few steps starting from simple imines 16 (Fig. 4, Scheme 9) [64,65,82-84], A special feature of these 5-membered ring carbenes is their stabibzation by the help of a quarternary carbon next to the carbene. [Pg.13]


See other pages where Cyclic alkyl is mentioned: [Pg.805]    [Pg.228]    [Pg.6]    [Pg.57]    [Pg.304]    [Pg.1074]    [Pg.470]    [Pg.272]    [Pg.70]    [Pg.141]    [Pg.92]    [Pg.12]    [Pg.16]    [Pg.528]    [Pg.220]    [Pg.752]    [Pg.51]    [Pg.324]    [Pg.10]    [Pg.11]    [Pg.23]    [Pg.67]    [Pg.116]    [Pg.323]    [Pg.353]   


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Alkyl nitronates cyclic nitronate preparation

Alkylation cyclic nitronate preparation

Alkylation of Cyclic Ethers

Alkylation of Cyclic Ketones and Related Compounds

Alkylation with Alcohols and Cyclic Ethers

Cyclic acetates, asymmetric allylic alkylations

Cyclic alkyl amino carbenes

Cyclic alkyl carbenes

Cyclic alkyl ligand

Cyclic allylic acetates, alkylation

Cyclic ethers alkylation with

Cyclic mechanism alkyl-substituted benzenes

Cyclic nitronates alkylation

Cyclic regiospecific alkylation

Cyclic, from alkyl halides

Lactams, alkylation cyclic ketones

Phosphorus, alkylation cyclic acids

Phosphorus, alkylation cyclic compounds

Ruthenium Olefin Metathesis Catalysts Supported by Cyclic Alkyl Aminocarbenes (CAACs)

Stereochemistry of Cyclic Ketone Alkylation

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