Samarium diiodide coupling of enones: a remarkable cascade sequence

[reaction: see text] Treatment of cyclic enones with SmI(2) in THF/MeOH (4:1) led to tricyclic diol products in one step and, in the case of enone 7, gave the tetracycle 13 as a single diastereoisomer in up to 67% yield.     

Transition metal salts-catalyzed aza-Michael reactions of enones with carbamates

Several transition metal salts were found to catalyze aza-Michael reactions of enones with carbamates efficiently. The catalytic activity was strongly dependent on the nature of the metal salts. While conventional Lewis acids such as BF(3).OEt(2), AlCl(3), or TiCl(4) showed lower activity, group 7-11 transition metal salts in higher oxidation states such as ReCl(5), Fe(ClO(4))(3).9H(2)O, RuCl(3).nH(2)O, OsCl(3).3H(2)O, RhCl(3).nH(2)O, PtCl(4).5H(2)O, or AuCl(3).H(2)O exhibited higher catalytic activity. [reaction: see text]     

Synthesis of ferrocene-substituted 2-azetidinones.

The photochemical reaction of alkoxychromium(0)carbene complexes and ferrocene mono- and disubstituted imines formed 2-azetidinones having one or two ferrocene moieties in good yields. Yields decrease when the carbene moiety bears an aminoferrocene moiety attached to the carbene carbon, while complex 9 having the ferrocene directly bonded to the carbene carbon was totally inert in these reactions. Access to beta-lactams with the ferrocene tethered to the C3 position through a methylene group was gained using the lithium enolate derived from ethyl 3-ferrocenylpropanoate. The reaction of this enolate produced two unexpected processes. Thus, 2-azetidinone 15 having an hydroxyl group at the C3 position was obtained together with the expected beta-lactam 14, by reaction of the lithium enolate of ethyl 3-ferrocenylpropenoate and imine 1. Additionally, unsaturated amide 17 was obtained by base-promoted Hoffmann-like breakage of the beta-lactam ring formed in the reaction of the same enolate and imine 2. Oxidation of the anion at the C3 of the 2-azetidinone ring on compound 14, as well as the sterically driven ring-breakage of the C3 anion derived from the nonisolated 2-azetidinone 18, should be responsible for this behavior.     

Samarium Barbier reactions of alpha-iodomethyloxazoles and thiazoles with aliphatic aldehydes

[reaction: see text] The reductive coupling of substituted alpha-iodomethyloxazoles and thiazoles with aliphatic aldehydes under Barbier conditions provides an effective method for the direct incorporation of intact heterocyclic systems.     

3+2] cycloaddition reactions of cyclopropyl imines with enones

A nickel-catalyzed [3+2] cycloaddition of cyclopropyl aldimines and enones has been developed. The process provides direct access to trisubstituted cyclopentanes, and the scope exceeds that of the corresponding reactions involving cyclopropyl ketones. A basis for the improved performance of cyclopropyl aldimines compared with cyclopropyl ketones is provided.     

Chiral Sc-catalyzed asymmetric Michael reactions of thiols with enones in water

Asymmetric Michael reactions of thiols with enones were catalyzed by a Sc(OTf)(3)-chiral bipyridine complex at room temperature in water without using any organic solvents, to afford the desired sulfides in high yields with high enantioselectivities.     

Kinetic analysis of sequential multistep reactions

Many processes in biology and chemistry involve multistep reactions or transitions. The kinetic data associated with these reactions are manifested by superpositions of exponential decays that are often difficult to dissect. Two major challenges have hampered the kinetic analysis of multistep chemical reactions: (1) reliable and unbiased determination of the number of reaction steps, and (2) stable reconstruction of the distribution of kinetic rate constants. Here, we introduce two numerically stable integral transformations to solve these two challenges. The first transformation enables us to deduce the number of rate-limiting steps from kinetic measurements, even when each step has arbitrarily distributed rate constants. The second transformation allows us to reconstruct the distribution of rate constants in the multistep reaction using the phase function approach, without fitting the data. We demonstrate the stability of the two integral transformations by both analytic proofs and numerical tests. These new methods will help provide robust and unbiased kinetic analysis for many complex chemical and biochemical reactions.     

Alpha'-hydroxy enones as achiral templates for Lewis acid-catalyzed enantioselective Diels-Alder reactions

alpha'-Hydroxy enones react with dienes in the presence of (S,S)-[Cu(tBu-box)](OTf)2 or (S,S)-[Cu(tBu-box)](SbF6)2 (2 to 10 mol %) to afford the corresponding Diels-Alder adducts in high yield and selectivity. Isomeric ratios (regioselectivity, endo/exo or cis/trans) of up to >99:1 and ee values of up to >99% are obtained. Significantly, difficult dienes such as isoprene, 2,3-dimethyl butadiene and piperylene behave satisfactorily. Subsequent oxidative cleavage of the ketol in the resulting cycloadducts by treatment with cerium ammonium nitrate (CAN) yields the corresponding enantiopure carboxylic acids. Alternatively, carbonyl addition and subsequent diol cleavage with CAN produces the corresponding ketone adducts.     

One-pot sequential Baylis-Hillman and Michael reactions

A new one-pot procedure for the sequential Baylis-Hillman and Michael reactions has been developed to construct two carbon-carbon bonds with three components. This procedure has been applied to combine a variety of aromatic aldehydes, β-unsubstituted acrylates and activated methide nucleophiles to generate highly diversified and functionalized organic compounds.     

Enantioselective Lewis acid-catalyzed Mukaiyama-Michael reactions of acyclic enones. Catalysis by allo-threonine-derived oxazaborolidinones

allo-Threonine-derived O-aroyl-B-phenyl-N-tosyl-1,3,2-oxazaborolidin-5-ones 1g,n catalyze the asymmetric Mukaiyama-Michael reaction of acyclic enones with a trimethylsilyl ketene S,O-acetal in high enantioselectivity. A range of alkenyl methyl ketones is successfully employed as Michael acceptors affording ee values of 85-90% by using 10 mol % of the catalyst. The use of 2,6-diisopropylphenol and tert-butyl methyl ether as additives is found to be essential to achieve high enantioselectivity in these reactions. The effects of the additives are discussed in terms of the retardation of an Si(+)-catalyzed racemic pathway, which seriously deteriorates the enantioselectivity of asymmetric Mukaiyama-Michael reactions. A working model for asymmetric induction is proposed based on correlation between catalyst structures and enantioselectivities.     

Efficient Baylis-Hillman reactions of cyclic enones in methanol as catalyzed by methoxide anion

The Baylis-Hillman reactions of cyclic enones with a variety of aldehydes were investigated. 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) was found to be a viable catalyst in promoting the reactions of sterically retarded substrates in methanol. The reactions showed clear solvent dependence and only occurred in hydroxylic solvents, especially in methanol. Further consideration on the steric character of DBU and its high basicity jointly with other experimental observations suggests that the methoxide anion should be the "true" Baylis-Hillman catalyst. This has been confirmed by the effectiveness of similar reactions directly employing methoxide as the catalyst. The reaction pathways of this type of catalysis are proposed to depend on the choice of substrates. Supporting experimental observations were demonstrated and discussed in relation to mechanistic considerations. This study also reveals that both DBU and sodium methoxide can be successfully applied as effective catalysts in methanol to promote the Baylis-Hillman reactions for a range of cyclic enones including cyclopent-2-enones, cyclohex-2-enones, gamma-pyrone, and 1-benzopyran-4(4H)-ones.     

Samarium(ii) iodide-mediated intramolecular pinacol coupling reactions with cyclopropyl ketones

The first reported intramolecular pinacol coupling of cyclopropyl ketones has been achieved, demonstrating that cyclisation competes favourably with ring-opening of the cyclopropyl ketyl radical.     

Self-assembled monolayers of ferrocene-substituted biphenyl ethynyl thiols on gold

Homogeneous and mixed [with biphenylthiol (BPT)] self-assembled monolayers (SAMs) of ferrocene-substituted biphenyl ethynyl thiols (Fc) were prepared on Au(111) substrates and characterized by several complementary spectroscopic techniques. The mixed films were fabricated either by subsequent immersion of the substrates into the BPT and Fc solutions or by immersion of the substrate into a mixed solution of BPT and Fc. The first procedure resulted in the preparation of high-quality mixed SAMs, in which the Fc molecules were stochastically distributed in the BPT matrix and well-separated from each other. The portion of these molecules in such films could be precisely varied from ca. 7 to 42% by selection of the immersion time in the BPT solution. The films prepared from the mixed solution exhibited a phase separation between the Fc and BPT constituents. These films contained mostly the Fc molecules ( approximately 80-90%), showing, thus, a significant deviation from the relative content of the target molecules in the primary solution (a 1:1 ratio). This finding shows that the Fc molecules, when competing with BPT, preferably adsorb onto Au(111) substrate, suggesting a significant impact of the ferrocene groups onto the structure-building interactions responsible for molecular self-assembly.     

Cesium fluoride mediated intramolecular conjugate-addition reactions of alpha sulfonyl ester to enones and alpha-chloroenones

Cesium fluoride is a useful catalyst to effect the intramolecular conjugate-addition of alpha-sulfonyl esters to enones; similar reaction with alpha-chloroenones provides fused cyclopropane adducts.     

An efficient and inexpensive catalyst system for the aza-Michael reactions of enones with carbamates

A new strategy which uses very cheap FeCl3 as an effective catalyst in the presence of Me3SiCl has been developed for the conjugate addition of enones and chalcone with unactivated weakly nucleophilic carbamates.     

Cooperative effects in random sequential polymer reactions

We consider the kinetics of a reaction in a polymer system where each reacted unit protects its (r—1)-nearest neighbours completely against reaction and modifies the reactivity of the r-nearest neighbours. The number of sequences containing a specified numberof unreacted units, together with the over-all extent of reaction, is determined as function of time. In a continuum limit the model also describes the time evolution of a sequential filling of hard rods on a line