Transition cyclic

It was reported recently [216] that optical-quality PbTe thin films can be directly electrodeposited onto n-type Si(lOO) substrates, without an intermediate buffer layer, from an acidic (pH 1) lead acetate, tellurite, stirred solution at 20 °C. SEM, EDX, and XRD analyses showed that in optimal deposition conditions the films were uniform, compact, and stoichiometric, made of fine, 50-100 nm in size, crystallites of a polycrystalline cubic structure, with a composition of 51.2 at.% Pb and 48.8 at.% Te. According to optical measurements, the band gap of the films was 0.31 eV and of a direct transition. Cyclic voltammetry indicated that the electrodeposition occurred via an induced co-deposition mechanism. 

The above reaction proceeds via a transition cyclic intermediate. 

In a more recent paper, optically pure 5-bromo-2-hydro) entanenitrile silyl ether 108 was treated with several different arylmagnesium bromides to afford, after reduction with NaBH4 (the transitional cyclic imine was unstable, thus it had to be reduced in situ), the desired piperidine derivatives as practically single diastereo-isomers (Scheme 20). 

Fig. 3 Possible course of the addition of hydride anion to the transitional cyclic imine.

Simplest examples are prepared by the cyclic oligomerization of ethylene oxide. They act as complexing agents which solubilize alkali metal ions in non-polar solvents, complex alkaline earth cations, transition metal cations and ammonium cations, e.g. 12—crown —4 is specific for the lithium cation. Used in phase-transfer chemistry. ... 

Adopting the view that any theory of aromaticity is also a theory of pericyclic reactions [19], we are now in a position to discuss pericyclic reactions in terms of phase change. Two reaction types are distinguished those that preserve the phase of the total electi onic wave-function - these are phase preserving reactions (p-type), and those in which the phase is inverted - these are phase inverting reactions (i-type). The fomier have an aromatic transition state, and the latter an antiaromatic one. The results of [28] may be applied to these systems. In distinction with the cyclic polyenes, the two basis wave functions need not be equivalent. The wave function of the reactants R) and the products P), respectively, can be used. The electronic wave function of the transition state may be represented by a linear combination of the electronic wave functions of the reactant and the product. Of the two possible combinations, the in-phase one [Eq. (11)] is phase preserving (p-type), while the out-of-phase one [Eq. (12)], is i-type (phase inverting), compare Eqs. (6) and (7). Normalization constants are assumed in both equations ... 

Step 2 of the mechanism m Figure 6 12 is a nucleophilic attack by Br at one of the carbons of the cyclic bromonium ion For reasons that will be explained m Chapter 8 reactions of this type normally take place via a transition state m which the nude ophile approaches carbon from the side opposite the bond that is to be broken Recall mg that the vicinal dibromide formed from cyclopentene is exclusively the trans stereoisomer we see that attack by Br from the side opposite the C—Br bond of the bromonium ion intermediate can give only trans 1 2 dibromocyclopentane m accordance with the experimental observations... 

The Diels-Alder cycloaddition is one example of a pencyclic reaction, which is a one step reaction that proceeds through a cyclic transition state Bond formation occurs at both ends of the diene system and the Diels-Alder transition state involves a cyclic array of six carbons and six tt electrons The diene must adopt the s cis conformation m the transition state... 

The transition state incorporates a cyclic array of six atoms... 

Cyanohydrins are formed by nucleophilic addition of HCN to the carbonyl group of an aldehyde or a ketone Cycloadd ition (Section 10 12) Addition such as the Diels-Alder reaction in which a ring is formed via a cyclic transition state... 

The bond highlighted m yellow is the peptide bond ) Pencyclic reaction (Section 10 12) A reaction that proceeds through a cyclic transition state Period (Section 1 1) A honzontal row of the penodic table Peroxide (Section 6 8) A compound of the type ROOR Peroxide effect (Section 6 8) Reversal of regioselectivity oh served m the addition of hydrogen bromide to alkenes brought about by the presence of peroxides m the reaction mixture... 

When fragmentation is accompanied by the formation of a new bond as well as by the breaking of an existing bond, a rearrangement process is involved. These will be even mass peaks when only C, H, and O are involved. The migrating atom is almost exclusively hydrogen six-membered cyclic transition states are most important. 

AUylic organoboranes react via cyclic transition states not only with aldehydes and ketones, but also with alkynes, aHenes, and electron-rich or strained alkenes. Bicyclic stmctures, which can be further transformed into boraadamantanes, are obtained from triaHyl- or tricrotylborane and alkynes (323,438,439). 

An unusual addition of acetoacetic acid to pyrido[2,3-Z>]pyrazin-2(l//)-one (400) to give (eventually) the 3-acetonyl derivative (401) was postulated (71TH21500) to occur via a cyclic transition state, and the similar addition of oxalacetic ester may occur via a related mechanism. 

REACTIONS WITH CYCLIC TRANSITION STATES 5.02.9.1 Cycloadditions... 

The advantage of starting with a ring of -1 members lies in the nature of the rearrangements, which proceed through cyclic transition states, so that the system never becomes open-chain — the carbon-carbon bond is broken only while the carbon-heteroatom bond is being made. 

---