In the golden age of organocatalysis

The term "organocatalysis" describes the acceleration of chemical reactions through the addition of a substoichiometric quantity of an organic compound. The interest in this field has increased spectacularly in the last few years as result of both the novelty of the concept and, more importantly, the fact that the efficiency and selectivity of many organocatalytic reactions meet the standards of established organic reactions. Organocatalytic reactions are becoming powerful tools in the construction of complex molecular skeletons. The diverse examples show that in recent years organocatalysis has developed within organic chemistry into its own subdiscipline, whose "Golden Age" has already dawned.     

Enantioselective Oxidation of Sulfides Catalyzed by Chiral MoV and CuII Complexes of Catechol-Appended β-Cyclodextrin Derivatives in Water

The two modified β-cyclodextrin (β-CD) derivatives having catechol-type ligand (2,3- and 3,4-dihydroxy groups on the benzoate ring) were synthesized. The chiral catalytic activity of their Mo^V and Cu^II complexes was examined in the asymmetric oxidation of aromatic sulfides using hydrogen peroxide in water (pH 6.0). The oxidation with the Mo^V complexes of two β-CD derivatives were more accelerated than that with the Cu^II complexes. The sign of the optical rotation of the sulfoxides obtained in the above two cases showed the opposite configuration in the oxidation of the same sulfide. The difference of the enantioselectivity appeared also between the two complexes of the 2,3- and 3,4-dihydroxybenzoate derivatives with the same metal ion. While the use of the Mo^V complexes with the catechol derivatives yielded the sulfoxides with 35–65% ee, the use of the Cu^II complexes gave the products with the␣opposite configuration at 26–52% ee. The chiral induction in the oxidation, observed conversely between the␣catalysts, was reflected on the chiral conformation of the respective metal catalysts, showed in Induced Circular Dichroism (ICD) spectra. The highest optical yield, 65%, was observed in the oxidation of butyl phenyl sulfide using the catalytic amount (0.1 equiv) of the Mo^V complex with mono-6-O-(3,4-dihydroxybenzoyl)-β-CD. The reaction gave predominantly the (S)-sulfoxide in 95% chemical yield.     

Asymmetric multicomponent reactions (AMCRs): the new frontier

Asymmetric multicomponent reactions involve the preparation of chiral compounds by the reaction of three or more reagents added simultaneously. This kind of addition and reaction has some advantages over classic divergent reaction strategies, such as lower costs, time, and energy, as well as environmentally friendlier aspects. All these advantages, together with the high level of stereoselectivity attained in some of these reactions, will force chemists in industry as in academia to adopt this new strategy of synthesis, or at least to consider it as a viable option. The positive aspects as well as the drawbacks of this strategy are discussed in this Review.     

Stereocontrol in Organic Synthesis Using the Diphenylphosphoryl Group

In 1959, Horner showed that metalated alkyldiphenylphosphane oxides react with aldehydes or ketones to give alkenes. With this reaction, the diphenylphosphoryl (Ph₂PO) group made its entrance into synthetic organic chemistry. In the thirty-six years since that date, extensive research has shown that this olefination, the Horner–Wittig reaction, has unique properties that make it much more than simply the phosphane oxide cousin of the more famous phosphorus-based olefinations—the Wittig reaction (based on phosphonium salts) and the Wadsworth–Emmons reaction (based on phosphonate esters). Early work on the Horner–Wittig reaction concentrated on the reactivity of phosphane oxides and the regioselectivity of their reactions, but more recently the power of the Ph₂PO group to control the stereochemistry of alkenes, and to produce “on demand” either stereoisomer in high stereochemical purity, has emerged. From the study of these stereocontrolled Horner–Wittig reactions arose the realization that the Ph₂PO group is useful not only for the control of the two-dimensional stereochemistry of alkenes, but also of three-dimensional stereochemistry in general. After a brief introduction to phosphane oxide chemistry, this review will examine the Horner–Wittig reaction, in both its original and “stereocontrolled” varieties. From there, we will move on to an account of the stereoselective construction of molecules containing the Ph₂PO group, concentrating on the stereochemical directing effects of the Ph₂PO group and on the role of its unique combination of attributes—steric bulk, electronegativity, and Lewis basicity—in controlling these reactions. Finally, we will present what is intended as a practical guide to this chemistry, covering the type of functionalized alkenes that have been made with the help of the Ph₂PO group and giving guidelines that we hope will help the organic chemist to make the most of the chemistry the Ph₂PO group has to offer.     

烯丙基二异雪松基硼烷的制备及其与羰基化合物的不对称反应

本文以(-)-α-雪松烯为原料, 制备了烯丙基二异雪松基硼烷(Icd~2B-CH~2CH=CH~2). 该手性硼烷很容易与醛反应生成相应的烯丙基取代的手性仲醇, 光学产率在60%e.e.左右. 与潜手性酮反应的光学产率低于30%e.e..     

A Versatile Approach for the Asymmetric Synthesis of 3-Alkyl-isoindolin-1-ones

3 Ｓｕｂｓｔｉｔｕｔｅｄｉｓｏｉｎｄｏｌｉｎ 1 ｏｎｅｓ (2 ,3 ｄｉｈｙｄｒｏ 1Ｈ ｉｓｏｉｎｄｏｌｉｎ 1 ｏｎｅｓ)ｏｆｇｅｎｅｒａｌｓｔｒｕｃｔｕｒｅ (1)ｃｏｎｓｔｉｔｕｔｅｔｈｅｋｅｙｓｔｒｕｃｔｕｒａｌｆｅａｔｕｒｅｏｆａｌａｒｇｅｎｕｍｂｅｒｏｆｂｉｏａｃｔｉｖｅｍｏｌｅｃｕｌｅｓｏｆｎａｔｕｒａｌｏｒｓｙｎｔｈｅｔｉｃｏｒｉｇｉｎ .Ｆｏｒｅｘａｍｐｌｅ ,ｌｅｎｎｏｘａｍｉｎｅ (2 ) ,1ｎｕｅｖａｍｉｎｅａｎｄｃｈｉｌｅｎｉｎｅａｒｅａｌｋａｌｏｉｄｓｉｓｏｌａｔｅｄｆｒｏｍｖａｒｉｏｕｓ…     

New optically active organoantimony (BINASb) and bismuth (BINABi) compounds comprising a 1,1′-binaphthyl core: synthesis and their use in transition metal-catalyzed asymmetric hydrosilylation of ketones

Racemic 2,2′-bis[diarylstibano]-1,1′-binaphthyls [(±)-BINASbs] and 2,2′-bis[di(p-tolyl)bismuthano]-1,1′-binaphthyl [(±)-BINABi], which are the antimony and bismuth congeners of BINAP, have been prepared from 2,2′-dibromo-1,1′-binaphthyl (DBBN) via 2,2′-dilithio-1,1′-binaphthyl intermediate by treatment with the appropriate metal halides [(p-Tol)₂SbBr, Ph₂SbBr and (p-Tol)₂BiCl]. The optical resolution of the (±)-BINASbs could be achieved via the separation of a mixture of the diastereomeric Pd-complexes derived from the reaction of (±)-BINASbs with di-μ-chlorobis{(S)-2-[1-(dimethylamino)-ethyl]phenyl-C¹,N}dipalladium(II). Optically active (R)-BINASb and (R)-BINABi could be also obtained from optically active (R)-DBBN by the same procedure. The enantiopure BINASbs have been shown to be effective chiral ligands for the rhodium-catalyzed asymmetric hydrosilylation of ketones.     

Synthesis and Asymmetric Enantioselective Addition of Chiral Polybinaphthyl and Polybinaphthol I.igands

Four chiral polymers P-1, P-2, P-3 and P-4 were synthesized by the polymerization of （S）-2,2＇-dioctoxy-1,1＇- binaphthyl-6,6＇-boronic acid （S-M-3） with （S）-6,6＇-dibromo-1,1＇-binaphthol （S-M-1）, （R）-6,6＇-dibromo-1,1＇- binaphthol （R-M-1）, （S）-3,3＇-diiodo-1,1＇-binaphthol （S-M-2） and （R）-3,3＇-diiodo-1,1＇-binaphthol （R-M-2） under Pd-catalyzed Suzuki reaction, respectively. All four polymers can show good solubility in some common solvents due to the nonplanarity of the polymers in the main chain backbone and flexible alkyl groups in the side chain. The analysis results indicate that specific rotation and circular dichroism （CD） spectral signals of the alternative S-S chiral polymers P-1 and P-3 are larger than those of S-R chiral polymers P-2 and P-4, but their UV-Vis and fluorescence spectra are almost similar. The results of asymmetric enantioselectivity of four polymers for diethylzinc addition to benzaldehyde indicate that catalytically active center is （R） or （S）-1, 1＇-binaphthol moieties.     

Highly selective palladium catalyzed kinetic resolution and enantioselective substitution of racemic allylic carbonates with sulfur nucleophiles: asymmetric synthesis of allylic sulfides,allylic sulfones,and allylic alcohols

We describe the highly selective palladium catalyzed kinetic resolutions of the racemic cyclic allylic carbonates rac-1 a-c and racemic acyclic allylic carbonates rac-3 aa and rac-3 ba through reaction with tert-butylsulfinate, tolylsulfinate, phenylsulfinate anions and 2-pyrimidinethiol by using N,N'-(1R,2R)-1,2-cyclohexanediylbis[2-(diphenylphosphino)-benzamide] (BPA) as ligand. Selectivities are expressed in yields and ee values of recovered substrate and product and in selectivity factors S. The reaction of the cyclohexenyl carbonate 1 a (>/=99 % ee) with 2-pyrimidinethiol in the presence of BPA was shown to exhibit, under the conditions used, an overall pseudo-zero order kinetics in regard to the allylic substrate. Also described are the highly selective palladium catalyzed asymmetric syntheses of the cyclic and acyclic allylic tert-butylsulfones 2 aa, 2 b, 2 c, 2 d and 4 a-c, respectively, and of the cyclic and acyclic allylic 2-pyrimidyl-, 2-pyridyl-, and 4-chlorophenylsulfides 5 aa, 5 b, 5 ab, 6 aa-ac, 6 ba and 6 bb, respectively, from the corresponding racemic carbonates and sulfinate anions and thiols, respectively, in the presence of BPA. Synthesis of the E-configured allylic sulfides 6 aa, 6 ab, 6 ac and 6 bb was accompanied by the formation of minor amounts of the corresponding Z isomers. The analogous synthesis of allylic tert-butylsulfides from allylic carbonates and tert-butylthiol by using BPA could not be achieved. Reaction of the cyclopentenyl esters rac-1 da and rac-1 db with 2-pyrimidinethiol gave the allylic sulfide 5 c having only a low ee value. Similar results were obtained in the case of the reaction of the cyclohexenyl carbonate rac-1 a and of the acyclic carbonates rac-3 aa and rac-3 ba with 2-pyridinethiol and lead to the formation of the sulfides 5 ab, 6 ab, and 6 bb, respectively. The low ee values may be ascribed to the operating of a "memory effect", that is, both enantiomers of the substrate give the substitution product with different enantioselectivities. However, in the reaction of the racemic carbonate rac-1 a as well as of the highly enriched enantiomers 1 a (>/=99 % ee) and ent-1 a (>/=99 % ee) with 2-pyrimidinethiol the ee values of the substrates and the substitution product remained constant until complete conversion. Similar results were obtained in the reaction of the cyclic carbonates rac-1 a, ent-1 a (>/=99 % ee) and ent-1 c (>/=99 % ee) with lithium tert-butylsulfinate. Thus, in the case of rac-1 a and 2-pyrimidinthiol and tert-butylsulfinate anion as nucleophiles the enantioselectivity of the substitution step is, under the conditions used, independent of the chirality of the substrate; this shows that no "memory effect" is operating in this case. Hydrolysis of the carbonates ent-1 a-c, ent-3 aa and ent-3 ba, which were obtained through kinetic resolution, afforded the enantiomerically highly enriched cyclic allylic alcohols 9 a-c (>/=99 % ee) and acyclic allylic alcohols 10 a (>/=99 % ee) and 10 b (99 % ee), respectively.     

A vibrationally compensated far infrared laser interferometer for plasma density measurements

A modulated far-infrared laser interferometer which is presently operating on the PDX experiment at Princeton is described. The interferometer geometry permits the characterization of inside D, outside D as well as circular discharges. To achieve this versatility, a titanium corner cube reflector, mounted inside the PDX vacuum vessel is used in conjunction with a second visible wavelength interferometer for vibration corrections. In addition, the use of room temperature quasi-optical Schottky diodes in the far-infrared interferometer is reported. The minimum detectable line average density of the system is 5×10¹¹ cm^–3.