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John R Scheffer

Publications and source records attributed to John R Scheffer.

15 recordsLinked to original sources
PubMed2006

Monitoring structural transformations in crystals. 8. Monitoring molecules and a reaction center during a solid-state Yang photocyclization.

Structural changes taking place in a crystal during an intramolecular photochemical reaction [the Yang photocyclization of the alpha-methylbenzylamine salt with 1-(4-carboxybenzoyl)-1-methyladamantane] were monitored step-by-step using X-ray structure analysis. This is the first example of such a study carried out for an intramolecular photochemical reaction. During the photoreaction, both the reactant and product molecules change their orientation, but the reactant changes more rapidly after the reaction is about 80% complete. The distance between directly reacting atoms in the reactant molecule is almost constant until about 80% reaction progress and afterwards decreases. The torsion angle defined by the reactant atoms that form the cyclobutane ring also changes in the final stages of the photoreaction. These phenomena are explained in terms of the influence of many product molecules upon a small number of reacting molecules. The adamantane portion shifts more than the remaining part of the anionic reactant species during the reaction, which is explained in terms of hydrogen bonding. The structural changes are accompanied by changes in the cell constants. The results obtained in the present study are compared with analogous results published for intermolecular reactions.

Journal Article↗
PubMed2005

Photochemistry of 1-isopropylcycloalkyl aryl ketones: ring size effects, medium effects, and asymmetric induction.

[reaction: see text] The n = 0, 1, and 2 ketones shown above undergo Yang photocyclization in solution, but only the n = 1 analogues react this way in the solid state. Based on X-ray crystallography, these differences in reactivity are attributed to an unusually large distance for 1,4-hydroxybiradical cyclization in the solid state for the n = 0 and 2 ring systems, which leads to predominant reverse hydrogen transfer (rht). Enantiomeric excesses of up to 99% can be achieved in the case of the n = 1 system through the use of the solid-state ionic chiral auxiliary method of asymmetric synthesis.

Journal Article↗
PubMed2005

Asymmetric synthesis of dihydrofurans via a formal retro-Claisen photorearrangement.

Solution-phase irradiation of a series of syn-7-benzoylnorbornene derivatives is shown to lead to cis-fused dihydrofuran derivatives in low quantum but excellent chemical yields in what is formally a retro-Claisen rearrangement. In analogy to the well-known Paterno-Buchi reaction, the first step of the rearrangement is suggested to involve (n,pi)(3)-mediated addition of the carbonyl oxygen to the norbornene double bond, producing a triplet 1,4-biradical. This intermediate, rather than closing to the oxetane, undergoes cleavage accompanied by intersystem crossing to form the dihydrofuran. To determine whether the retro-Claisen photorearrangement could be carried out enantioselectively, the 7-benzoylnorbornene reactant was equipped with a para-carboxylic acid substituent to which a series of optically pure amines was attached ionically via salt bridges. Irradiation of these salts in the crystalline state followed by diazomethane workup (the solid-state ionic chiral auxiliary method) was shown to afford the corresponding dihydrofuran in optical yields as high as 93% at 95% conversion. X-ray crystallography revealed that the enantioselectivity arises from crystallization of the reactant in a conformation in which the carbonyl oxygen is more favorably oriented for bond formation to one end of the norbornene double bond than the other, thus leading to a predominance of a single enantiomer.

Crystallography, X-Ray↗
PubMed2004

Enantioselective photochemical synthesis of a simple alkene via the solid state ionic chiral auxiliary approach.

Irradiation of cis-bicyclo[4.3.0]non-8-ylacetophenone derivatives (1) in solution and the solid state yields cis-3a,4,5,6,7,7a-hexahydro-1H-indene (2) via a Norrish type II cleavage process. Asymmetric induction studies were conducted by providing the reactants with carboxylic acid substituents to which ionic chiral auxiliaries were attached through salt formation with optically pure amines. Irradiation of the salts (5 in total) in the crystalline state gave enantiomeric excesses of up to 44%. Single-crystal X-ray diffraction studies were performed on ketone 1a as well as salts 1d and 1g, and on this basis, the structure-reactivity relationships involved are discussed.

Journal Article↗
PubMed2004

1,4-hydroxybiradical behavior revealed through crystal structure-solid-state reactivity correlations.

Structure-reactivity correlations for triplet 1,4-hydroxybiradicals in solution are made difficult by the presence of multiple reactive conformers and the possibility of conformation-dependent intersystem crossing. These problems can be overcome by working in the crystalline state, where the conformations of the 1,4-hydroxybiradicals are fixed and determinable by X-ray crystallography of the parent ketones, assuming that hydrogen atom abstraction occurs with little or no change in conformation. This approach is applied to 15 bi- and tricyclic ketones designed to have slightly different biradical conformations, so that the effect of small and incremental changes in geometry on biradical behavior can be tested. The results indicate that, while geometry does have a strong influence on 1,4-hydroxybiradical partitioning between cyclization, cleavage, and reverse hydrogen transfer, a full understanding of the results requires that the strain involved in forming the cyclization products be taken into account.

Journal Article↗
PubMed2003

Thermal and photochemical transformation of conformational chirality into configurational chirality in the crystalline state.

Because they crystallize in chiral conformations in which abstraction of only one of two diastereotopic gamma-hydrogen atoms is possible, salts formed between achiral keto-acids possessing the tricyclo[4.4.1.0]undecane ring system and optically pure amines undergo Norrish type II cleavage in the solid state in enantiomeric excesses as high as 95% at 98% conversion, following removal of the ionic chiral auxiliaries. Thermal enolene rearrangement of the same salts results in optical yields approximately half those observed for the photochemical reaction.

Journal Article↗
PubMed2002

Enhanced enantio- and diastereoselectivity via confinement and cation binding: yang photocyclization of 2-benzoyladamantane derivatives within zeolites.

Irradiation of 2-benzoyladamantane derivatives in zeolites yields the endo-cyclobutanols as the only photoproduct via a gamma-hydrogen abstraction process. The cyclobutanols readily undergo retro-aldol reaction to give delta-ketoesters. The enantiomeric excess (ee) in the endo-cyclobutanols is measured by monitoring the ee in the ketoesters. Whereas in solution the ee in the product ketoester is zero, within achiral NaY zeolite, in the presence of a chiral inductor such as pseudoephedrine, ee's up to 28% have been obtained. The influence of zeolite on several chiral esters of 2-benzoyladamantane-2-carboxylic acids has also been examined. Whereas in solution the diastereomeric excess is <15%, in zeolite the delta-ketoesters are obtained in 79% de (best examples). Ab initio computations suggest that enhancement of chiral induction within zeolites is likely to be due to cation complexation with the reactant ketone. Alkali ion-organic interaction, a powerful tool, is waiting to be fully exploited in photochemical and thermal reactions. In this context zeolites could be a useful medium as one could view them as a reservoir of "naked" alkali ions that are only partially coordinated to the zeolite walls.

Journal Article↗
PubMed2002

Enhanced regioselectivity of Yang photocyclization in the crystalline state.

[reaction: see text] In contrast to the solution state, where Yang photocyclization of ketones of general structure 1 leads to equal amounts of cyclobutanols 2 and 3 (by abstraction of HA and HB, respectively), irradiation in the crystalline state is much more regioselective, favoring either 2 or 3 depending on the nature of the substituent X. X-ray crystallography and molecular mechanics calculations reveal the source of this remarkable solid-state regioselectivity.

Journal Article↗
PubMed2002

Use of chirally modified zeolites and crystals in photochemical asymmetric synthesis.

Three different approaches to asymmetric induction in the cis-to-trans photoisomerization of a number of 1-benzoyl-2,3-diphenylcyclopropane derivatives are reported: the use of chiral inductors and covalent chiral auxiliaries in MY zeolites and the use of ionic chiral auxiliaries in crystals. High levels of asymmetric induction were achieved using the latter two methods-up to 71% through the use of covalent chiral auxiliaries in zeolites and a remarkable 99% via the solid state ionic chiral auxiliary approach. In the zeolite method, the diastereomeric excess was found to depend strongly on the nature of the zeolite cation, M(+), and in the ionic chiral auxiliary approach, evidence is presented that it is the fixed orientation of the benzoyl group with respect to the cyclopropane ring that controls enantioselectivity in the crystalline state-a finding that is directly relevant to theoretical work on this topic.

Journal Article↗
PubMed2002

1-Methyl-5,6-diphenylpyrazine-2(1H)-thione.

The title compound, C(17)H(14)N(2)S, crystallizes in a triclinic unit cell, with two crystallographically independent molecules in the asymmetric unit. The two independent molecules pack in the same sense and form segregated layers along the c axis. The crystal is light-stable and no dimers are formed under irradiation. The intermolecular distances between the potential reactive centers (the C-3 and C-5 ring positions) are 4.093 (4) and 5.643 (4) A for molecule A, and 4.081 (4) and 5.614 (4) A for molecule B.

Journal Article↗