Selectivity lone pair

There are four main factors that affect the enantioselectivity of sulfur ylide-mediated reactions i) the lone-pair selectivity of the sulfonium salt formation, ii) the conformation of the resulting ylide, iii) the face selectivity of the ylide, and iv) betaine reversibility. 

For oxathiane 1, lone pair selectivity is controlled by steric interactions of the gem-dimethyl group and an anomeric effect, which renders the equatorial lone pair less nucleophilic than the axial lone pair. Of the resulting ylide conformations, 25a will be strongly preferred and will react on the more open Re face, since the Si face is blocked by the gem-dimethyl group (Scheme 1.9) [3, 15]. 

Figure 20.1 Lone pair-selectivity in the alkylation step.

The catalysts in Scheme 20.5 can be roughly divided into two classes non-C2-symmetric (1-6,12-13) and C2-symmetric (7-11) sulfides. In the initial alkylation step generating the sulfonium salts, a C2-symmetric sulfide can avoid the lone pair selectivity issue, as in this case the two lone pairs at the sulfur atom are identical. In contrast, the alkylation at the two diastereotopic lone pairs of the S atom in non-C2-symmetric sulfides would lead to the formation of two diastereoisomers of the sulfoniums. (Figure 20.1). This lone pair-selectivity can be reflected in the influence of the diastereomeric purity of preformed sulfonium salts on the enan-tioselectivity [7]. Several chiral sulfides (1-3 and 13) lacking Ci symmetry possess a similar camphor framework. 

The Michael addition of enamines to nitroalkenes proceeds with high Yyn selectivity. The Yyn selectivity is explained by an acyclic synclinal model, in which there is some favorable interaction between the nitro group and the nitrogen lone pair of the enamine group CEq. 4.67i. Both Z- and E-nitrostyrenes afford the same product in over 90% diastereoselecdvity. 

Stereochemistry can be influenced strongly by both catalyst and nonbonded interaction between an oxygen lone pair and nonadjacent n electrons, as illustrated by selected data of Ishiyama et al. (5d) (Table 2). 

In the case of sulfide 7 the bulky camphoryl moiety blocks one of the lone pairs on the sulfide, resulting in a single diastereomer upon alkylation. One of the conformations (29b) is rendered less favorable by non-bonded interactions such that conformation 29a is favored, resulting in the observed major isomer (Scheme 1.11). The face selectivity is also controlled by the camphoryl group, which blocks the Re face of the ylide. 

The lone pairs on the nitrogen and oxygen atoms make a significant difference in the chemical reactions (Scheme 17). P-Arylenamines undergo [2-t-2] cycloaddition reactions [93] whereas P-arylenol ethers undergo [2h-2h-2] cycloaddition reactions [94]. The mode selectivity was attributed [95] to the HOMO amplitude or the n bond polarity. 

Gleiter and Ginsburg found that 4-substituted-l,2,4-triazoline-3,5-dione reacted with the propellanes 36 and 37 at the syn face of the cyclohexadiene with respect to the hetero-ring. They ascribed the selectivity to the secondary orbital interaction between the orbitels (LUMO) of 36 and 37 with antisymmetrical combination of lone pair orbitals (HOMO ) of the triazolinediones (Scheme 24) [29]. 

Cieplak apphed this effect to the explanation of the shift of selectivity in the reactions of the pentamethylcyclopentadienes 21,19, and 20 having substiments of formyl, vinyl, and (hydroxyimino)methyl moiety at the 5-positions [14]. He pointed out that the observed result is consistent with the notion that in the case of formyl moiety the hyperconjugative effect is enhanced by lone pair back-donation due to ... 

They stated that the observed selectivity may be charge-controlled, since the molecular orbital calculation of the triazorine and the sulfone 95 showed a strongly negative field around the lone pairs of the azo moiety of the triazorine and a strongly positive field around the sulfur of the sulfone group [29]. 

The Jt-facial selectivity was explained by the Cieplak Effect due to back-donation of lone pair electrons on sulfur (Scheme 49). Mansuy and coworkers reported that in situ generated thiophene 1-oxide 99 could be trapped by 1,4-benzoqui-none to afford the corresponding syn attack product [58]. Tashiro and coworkers also reported that in situ generated thiophene 1-oxide derivatives 98,100-103 and... 

The condensation reactions described above are unique in yet another sense. The conversion of an amine, a basic residue, to a neutral imide occurs with the simultaneous creation of a carboxylic acid nearby. In one synthetic event, an amine acts as the template and is converted into a structure that is the complement of an amine in size, shape and functionality. In this manner the triacid 15 shows high selectivity toward the parent triamine in binding experiments. Complementarity in binding is self-evident. Cyclodextrins for example, provide a hydrophobic inner surface complementary to structures such as benzenes, adamantanes and ferrocenes having appropriate shapes and sizes 12) (cf. 1). Complementary functionality has been harder to arrange in macrocycles the lone pairs of the oxygens of crown ethers and the 7t-surfaces of the cyclo-phanes are relatively inert13). Catalytically useful functionality such as carboxylic acids and their derivatives are available for the first time within these new molecular clefts. 

This affinity for metals results not only from the structural organization of the new diacids but from stereoelectronic effects at carboxyl oxygen as well. The in-plane lone pairs of a carboxylate 18 differ in basicity by several orders of magnitude 16). Conventional chelating agents17> derived from carboxylic acids such as EDTA, 19a are constrained by their shape to involve the less basic anti lone pairs [Eq. (4)]. The new diacids are permitted the use of the more basic syn lone pairs in contact with the metal 19b. These systems represent a new type of chelate for highly selective recognition of divalent ions. 

The formation of 151 from the phosphonate 171 could be proved only by indirect means. Electron-rich aromatic compounds such as N,N-diethylaniline and N,N,N, N -tetraethyl-m-phenylenediamine U0 1I9> and N-methylaniline 120> are phosphorylated in the para- and in the ortho- plus para-positions by 151. Furthermore, 151 also adds to the nitrogen lone pair of aniline to form the corresponding phosphor-amidate. Considerable competition between nucleophiles of various strengths for the monomeric methyl metaphosphate 151 — e.g. aromatic substitution of N,N-diethylaniline and reaction with methanol or aromatic substitution and reaction with the nitrogen lone pair in N-methylaniline — again underline its extraordinary non-selectivity. 

Similar to nitrogen compounds, electron-rich sulfur compounds, such as the sulfides, with the lone pair of electrons on the sulfur atom, are oxidized to sulfoxides and, further, to sulfones by the H202/titanosilicate sytem (218,232, 233). Table XXXI (232) illustrates typical conversions and product selectivities for various sulfides for the reactions catalyzed by TS-1. Bulky sulfides such as alkyl, phenyl sulfides are relatively unreactive because of their steric exclusion from the pores of TS-1. Diphenyl sulfide could not be oxidized at all. As the diffusivity and, hence, the conversion of the sulfide decreases, the further oxidation of the primary product (sulfoxide) becomes more competitive, leading to increased formation of the corresponding sulfone (Table XXXI) ... 

Reduction of bulky organohalogermylenes leads to the formation of pentametallic germanium clusters 149 and 150 (Equations (260) and (261), respectively).322 The structure of 149 is shown in Figure 8, and selected structural data are collected in Table 32. The five germanium atoms are held together by six two-center, two-electron bonds, and a lone pair resides on the unsubstituted Ge(5) atom. 

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