Tetrahedron report number 646Multiple stereoselectivity and its application in organic synthesis
The broad applicability and efficiency of the multiple stereoselectivity is reviewed. The report contains 350 references.
Introduction
Stereoselectivity and stereoselective methods in organic synthesis are a problem of fundamental importance and will be even more important in the future as the drug industry is required to supply 100% optically pure compounds. Much progress in this area has been made in the last few years. A number of new, highly stereoselective reactions and methods have been developed and applied in industry.1., 2., 3., 4., 5. The Nobel Prize in chemistry has been awarded in 2001 to Sharpless, Noyori and Knowles for the development of catalytic asymmetric synthesis, selective processes and chiral catalysts.
One of the methods to increase the stereoselectivity of reactions is multiple stereoselectivity (multiple stereodifferentiation, multiple asymmetric induction), when the stereochemical process proceeds under the control of more than one chiral auxiliary. This kind of chemical transformation occurs in nature because many enzymatic reactions involve the cooperation of several chiral auxiliaries. This type of stereochemical effect, very important from a theoretical and practical standpoint, has not been sufficiently investigated.
In organic chemistry, the earliest attempts to increase the stereoselectivity of a reaction by means of two chiral auxiliaries were described, probably, by Vavon (1950),6 and Harada and Matsumoto (1966).7 In 1968, Horeau, Kagan and Vigneron8 discovered the cumulative effect of two auxiliaries in the reaction of phenyl glyoxalates to mandelate derivatives and named this effect as ‘the double induction’.
In 1977, Izumi9 has proposed the term ‘double stereo-differentiation’ which is more exact than the term ‘double asymmetric induction’. Articles devoted to the applications of double asymmetric synthesis in different sections of organic chemistry have been published. In 1984, the article of Poulin and Kagan10 being devoted to asymmetric hydrogenation and the section of Morrison's monograph written by Heathcock reviewing the aldol condensation.11 The following year, Masamune and co-authors12 described the application of double stereodifferentiation for four crucial reactions of organic chemistry: aldol condensation, hydrogenation, Sharpless epoxidation and Diels–Alder reactions.
During the past 10–15 years, this field of asymmetric synthesis was advanced and studies which allowed a consideration of the problems of stereodifferentiating reactions more widely and exactly have been performed. Multiple stereoselective reactions have found a use in such fields of organic chemistry as Sharpless dihydroxylation, Michael additions, addition to allylmetals, the Reformatsky reaction, the Mukaiyama reaction, photochemical reactions, alkylation, cycloadditions and the synthesis of heteroatom compounds, etc. New versions of multiple stereoselectivity were developed; the substrates, reagents and catalysts bearing several chiral auxiliaries with an additive effect of stereoselectivities, reacting under control of double asymmetric induction. These outstanding achievements require a generalisation of the existing information on the application of multiple asymmetric induction in organic synthesis and a critical consideration of a number of accumulated theoretical problems.
The present review describes the strategy which can be adopted to improve stereoselectivity. The aim of this review is to illustrate the processes to which these principles can be applied and the high degree of stereoselectivity which can be achieved.
The review summarises the progress which has been made and the current state of this field. It consists of two main parts treating the multiple stereodifferentiating reactions. The first part gives a stereochemical analysis of multiple asymmetric induction. The application of multiple stereodifferentiation as a method to increase the stereoselectivity of asymmetric reduction, oxidation, alkylation, addition to multiple bonds, enantioselective cycloaddition and synthesis of chiral heteroatom compounds are discussed in the second part. This part of the review emphasises the practical aspects of organic synthesis using multiple asymmetric induction. The present division of the review focuses on reactions having to demonstrate their potential uses in asymmetric synthesis.
Throughout this review, we employ the following abbreviations: Ac—acetyl, AI—asymmetric induction, All—Allyl, Ar—aryl group, Ar∗—aryl group containing an element of chirality, AD—asymmetric dihydroxylation, AE—asymmetric epoxidation, AS—asymmetric synthesis, BINAL-H—lithium (l,r-binaphthyl-2,2′-dioxy)ethoxy aluminium hydride, BINAP—2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, BPPM—(2S,4S)-butyl-4-(diphenylphosphino)-2-(diphenylphosphinomethyl)-1-(pyrrolidinecarboxylate), Boc—t-BuOCO, Bn—benzyl, Brn—Bornyl, Bz—benzoyl, Cat—catalyst, Cat∗—chiral catalyst, CHIRAPHOS—bis(diphenylphosphino)butane, COD—1,5-cyclooctadiene, Cy—cyclohexyl, ▵—heat, de—diastereomeric excess, ds—diastereoselectivity, dr—diastereomeric ratio, DET—diethyl tartrate, DIBAL—diisobutylaluminium hydride, DIOP—4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-dioxolane, DIPAMP—1,4-bis[O-methoxyphenyl(phenyl)phosphino]ethane, DIPHOS—1,2-bis(diphenylphosphino)ethane, DIPT—diisopropyl tartrate, DMSO—dimethylsulphoxide, ee—enantiomeric excess, Eu(fod)3—tris(6,6,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium, Eu(hfc)3—tris(3-heptafluoropropyl)hydroxymethylene)-d-camphorato]europium, HMPA—hexamethylphosphoric triamide, glc—glucosyl, Ipc—isopinocampheyl, dIpc—isopinocampheyl derived from (+)-α-pinene, llpc—isopinocampheyl derived from (−)-α-pinene, KHMDS—potassium hexamethyldisilazide, L—ligand, L∗—chiral ligand, LDA—lithium diisopropylamide, LHMDS—lithium hexamethyldisilazide, M—metal, Man—mannosyl, Mes—mesityl, Mnt—menthyl, (+)-Mnt—(1S,2R,5S)-menthyl, (−)-Mnt—(1R,2S,5R)-menthyl, MOM—methoxymethyl, Ms—methanesulphonyl, NaHMDS—sodium hexamethyldisilazide, Phth—phthalyl, RS, RM, RL—small, medium and large groups, R∗—alkyl or aryl group containing stereogenic centre or element of chirality, Ra-Ni—Raney nickel, Rha—rhamnosyl, S—substrate (starting material), TBDMS—t-butyldimethylsilyl, TBPS—t-butyldiphenylsilyl, THP—tetrahydropyran, Tf—trifluorosulphonyl, TMS—trimethylsilyl, THF—tetrahydrofuran, TFA—trifluoroacetic acid, X—group containing heteroatom, X∗—chiral auxiliary group.
Section snippets
Stereochemical analysis of multiple stereoselectivity
The stereoselectivity can be defined as the preferential formation of one product of several possible products that differ only in their configurations.1., 5. Stereoselectivity can be further subdivided into enantioselectivity and diastereoselectivity. According to Izumi,9 when the chirality of participating in differentiation occurs in a reagent, the catalyst or the reaction medium, the reaction is classified as an enantiodifferentiating reaction. When the chirality related to the
Multiple stereoselectivity as a method of stereocontrol in asymmetric organic synthesis
Multiple stereoselectivity as a method to increase the stereoselectivity has been more and more widely used in organic synthesis in the last few years, in order to find applications in new areas. During the last two decades, a number of powerful double stereoselective reactions have been developed as a result of the growing need to develop efficient and practical syntheses of biologically active compounds. Multiple stereoselective reactions provided an especially effective entry to the chiral
Conclusion and perspective of application
I hope that this review of multiple stereodifferentiating reactions and their application in organic synthesis will be useful to chemists interested in various aspects of chemistry and stereochemistry. The facts and problems discussed provide numerous possibilities for the study of additional stereochemical phenomena of stereoselective reactions and stereoselectivity.
Looking to the future, it may be said that the multiple asymmetric synthesis will be and should be the subject of future studies.
Oleg I. Kolodiazhnyi was born and grew up in Ukraine. He obtained his PhD (1969) and his Dr of Sci degree (1983) from the Kiev Institute of Organic Chemistry, National Academy of Sciences of Ukraine. Since 1990, he is the Head of Department of Physiologically Active Compound Synthesis in the Kiev Institute of Bioorganic Chemistry, National Academy of Sciences of Ukraine. In 1995, he obtained the Professor of Chemistry Diploma. His current interest is chemistry of organophosphorus compounds,
References (326)
- et al.
Tetrahedron
(1999) - et al.
Tetrahedron: Asymmetry
(1998)et al.J. Organomet. Chem.
(1996)et al.Tetrahedron: Asymmetry
(2001) - et al.
Chem. Rev.
(1998)et al.Chimie Nouvelle
(1991) - et al.
J. Org. Chem.
(1981) - et al.
Synth. Commun.
(1993)et al.J. Am. Chem. Soc.
(1992) - et al.
Tetrahedron: Asymmetry
(2001) - et al.
J. Mol. Catal. A: Chem.
(1999) - et al.
Synthesis
(1991) - et al.
Tetrahedron Lett.
(1988) - et al.
Synlett
(1995)
J. Org. Chem.
J. Am. Chem. Soc.
J. Am. Chem. Soc.
Tetrahedron Lett.
Tetrahedron: Asymmetry
J. Am. Chem. Soc.
Angew. Chem. Int. Ed. Engl.
J. Chem. Soc. Chem. Commun.
Tetrahedron Lett.
Pure Appl. Chem.
Tetrahedron: Asymmetry
J. Org. Chem.
J. Am. Chem. Soc.
Selectivity in Organic Synthesis
Stereoslective Synthesis
Stereoselective Synthesis in Organic Synthesis
Asymmetric Synthesis
C. R. Acad. Sci.
J. Org. Chem.
Bull. Soc. Chim. Fr.
Stereodifferentiating Reactions
J. Chem. Soc., Chem. Commun.
Angew. Chem.
J. Am. Chem. Soc.
Chiral Auxiliaries and Ligands in Asymmetric Synthesis
Bull. Soc. Chim. Fr.
J. Org. Chem.
Tetrahedron
Isr. J. Chem.
Tetrahedron: Asymmetry
Bull. Chem. Soc. Jpn
Bull. Chem. Soc. Jpn
J. Org. Chem.
Tetrahedron
Chem. Lett.
Gazz. Chim. Ital.
J. Organomet. Chem.
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Oleg I. Kolodiazhnyi was born and grew up in Ukraine. He obtained his PhD (1969) and his Dr of Sci degree (1983) from the Kiev Institute of Organic Chemistry, National Academy of Sciences of Ukraine. Since 1990, he is the Head of Department of Physiologically Active Compound Synthesis in the Kiev Institute of Bioorganic Chemistry, National Academy of Sciences of Ukraine. In 1995, he obtained the Professor of Chemistry Diploma. His current interest is chemistry of organophosphorus compounds, synthesis of new highly reactive phosphorus compounds and reagents. He is also studying asymmetric synthesis, asymmetric catalysis, diastereo- and enantioselective reactions and new synthetic strategies for the synthesis of biologically active compounds. He is currently a member of the Editorial Board of the Journal of Phosphorus, Sulfur and Silicon. He was awarded the Kiprianov Prize, the highest award of the Ukrainian National Academy of Sciences in Organic Chemistry. His scientific studies were supported by many national and international grants. He is the author of 300 publications and patents, including several monographs, a number of reviews and chapters in books.