Base substitution, stereochemistry

With the advent of techniques such as this, I believe that in the next ten years our understanding of substitution kinetics is going to take a giant step forward. We are going to be able to make observations which the organic chemist is able to make now, that is, take an instantaneous snapshot of the relative arrangement of the atoms in the complex, and draw mechanistic conclusions based on stereochemistry. 

An unexpected product was obtained when the o-phenylene diamine 437 was reacted with an excess of the Mannich base, -substituted 3-dimethylaminopropiophenone hydrochloride. A product, whose relative stereochemistry was determined by NMR, was shown to have structure 438 (Equation 66) <2000EJ01973>. 

The wM-diacetate 363 can be transformed into either enantiomer of the 4-substituted 2-cyclohexen-l-ol 364 via the enzymatic hydrolysis. By changing the relative reactivity of the allylic leaving groups (acetate and the more reactive carbonate), either enantiomer of 4-substituted cyclohexenyl acetate is accessible by choice. Then the enantioselective synthesis of (7 )- and (S)-5-substituted 1,3-cyclohexadienes 365 and 367 can be achieved. The Pd(II)-cat-alyzed acetoxylactonization of the diene acids affords the lactones 366 and 368 of different stereochemistry[310]. The tropane alkaloid skeletons 370 and 371 have been constructed based on this chemoselective Pd-catalyzed reactions of 6-benzyloxy-l,3-cycloheptadiene (369)[311]. 

Although not of industrial importance, many organometallic approaches have been developed (38). A one-pot synthesis of vitamin has been described and is based on the anionic [4 + 2] cycloaddition of three-substituted isoben2ofuranones to l-phytyl-l-(phenylsulfonyl)propene. Owing to the rather mild chemical conditions, the (H)-stereochemistry is retained (39). 

A wide variety of /3-lactams are available by these routes because of the range of substituents possible in either the ketene or its equivalent substituted acetic acid derivative. Considerable diversity in imine structure is also possible. In addition to simple Schiff bases, imino esters and thioethers, amidines, cyclic imines and conjugated imines such as cinnamy-lidineaniline have found wide application in the synthesis of functionalized /3-lactams. A-Acylhydrazones can be used, but phenylhydrazones and O-alkyloximes do not give /3-lactams. These /3-lactam forming reactions give both cis and /raMS-azetidin-2-ones some control over stereochemistry can, however, be exercised by choice of reactants and conditions. 

The silicon- and sulfur-substituted 9-allyl-9-borabicyclo[3.3.1]nonane 2 is similarly prepared via the hydroboration of l-phenylthio-l-trimethylsilyl-l,2-propadiene with 9-borabicy-clo[3.3.1]nonane36. The stereochemistry indicated for the allylborane is most likely the result of thermodynamic control, since this reagent should be unstable with respect to reversible 1,3-borotropic shifts. Products of the reactions of 2 and aldehydes are easily converted inlo 2-phenylthio-l,3-butadienes via acid- or base-catalyzed Peterson eliminations. 

Scheme 36 RCM-based synthesis of aspicilin (189) effect of substrate substitution on regio-and stereochemistry [93]...

Asymmetric syntheses of warfarin <96TL8321> and the axially chiral bicoumarin, isokotanin A <96TL3015> have been reported. The former is based on a Rh-catalysed asymmetric hydrogenation of a 3-(a,P-unsaturated ketone) substituted coumarin, whilst the key steps of the latter are an asymmetric Ullmann coupling and a selective demethylation. The stereochemistry of the fused dihydrocoumarin resulting from Li/NHs reduction of... 

Acyclic Ketones. The stereochemistry of the reduction of acyclic aldehydes and ketones is a function of the substitution on the adjacent carbon atom and can be predicted on the basis of the Felkin conformational model of the TS,63 which is based on a combination of steric and stereoelectronic effects. 

As previously mentioned, the nucleophilic substitution on the Mo complex 71 most likely occurs with retention of configuration based on the stereochemistry outcomes of the product and 71. The retention-retention mechanism was confirmed with labeling experiments in collaboration with Professor Lloyd-Jones, as shown in Scheme 2.25 [27]. 

Solvolysis of the propargyl chlorides E- and Z-24 (stereochemistry based on Cl and Ph25) in 80% aqueous ethanol at 50 °C gave, besides the corresponding solvent captured substituted propargyl products, the allenyl chlorides E- and Z-25 formed with complete retention via the allenyl cation intermediate (equation 6)25. 

Independent evidence for backside attack in gas-phase acid-induced nucleophilic substitutions was provided by a number of studies, carried out using stationary radiolysis." Further confirmation was provided by Morton and coworkers," who investigated the stereochemistry of the proton-induced nucleophilic substitution on (5)-(- -)- and (R)-(— )-2-butanol in the gas-phase at 10 torr in their 70-eV EBF radiolysis reactor. In the presence of a strong base, i.e., tri-n-propylamine... 

The oxidation of enol ethers at a reticulated vitreous carbon anode [2, 3] (Scheme 1) in a mixture of methanol/THF containing tetraethylammonium tosylate as the electrolyte and 2,6-lutidine as the base leads to substituted tetrahydrofu-ran and tetrahydropyran rings in good yields (51-96%). The major product obtained had a trans-stereochemistry. The cyclization failed to make seven-membered ring products. In order to determine the... 

To explain the stereochemistry of the allylic substitution reaction, a simple stereoelectronic model based on frontier molecular orbital considerations has been proposed (155, Fig. 6.2). Organocopper reagents, unlike C-nucleophiles, possess filled d-orbitals (d configuration), which can interact both with the 7t -(C=C) orbital at the y-carbon and to a minor extent with the o- -(C-X) orbital, as depicted... 

Fig. 6.2. Frontier orbital-based model to explain the stereochemistry of allylic substitution.

In addition to the presence of these elements in ores, they are also available from recycled feeds, such as catalyst wastes, and as an intermediate bulk palladium platinum product from some refineries. The processes that have been devised to separate these elements rely on two general routes selective extraction with different reagents or coextraction of the elements followed by selective stripping. To understand these alternatives, it is necessary to consider the basic solution chemistry of these elements. The two common oxidation states and stereochemistries are square planar palladium(II) and octahedral platinum(IV). Of these, palladium(II) has the faster substitution kinetics, with platinum(IV) virtually inert. However even for palladium, substitution is much slower than for the base metals so long as contact times are required to achieve extraction equilibrium. 

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