Über die Autorin bzw. den Autor

TSE-LOK HO is Professor of Organic Chemistry at National Chiao Tung University in Taiwan. His research interests are in organic synthesis, including total synthesis of natural products and methodology. He has written 26 books, including, most recently, Stereoselectivity in Synthesis, available from Wiley. Dr. Ho holds degrees from National Taiwan University and the University of New Brunswick, Canada.

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From reviews of previous volumes:

"Essential for chemistry collections at the university and research levels."
―New York Public Library

"Highly recommended...lots of succinct, practical information on recent developments...in a format that is easy to use. The reagents are taken up in alphabetical order (common usage names, not CAS indexing code names), sometimes several to a page, sometimes several pages to a reagent. One can expect to find how to make the reagent (in loose terms), or where it can be bought, what it is good for, and where to seek complete details. As with previous volumes, one can profit from just browsing, even if one does not feel a need to look up any particular subject. It is thus a secondary function of the book to help one keep abreast of the field, and it would be a rare chemist who would not learn something new and useful from a casual perusal of the pages."
―Journal of the American Chemical Society

REAGENTS FOR ORGANIC SYNTHESIS
Volume 1 1967 (0-471-25875-X) 1,475 pp.
Volume 2 1969 (0-471-25876-8) 538 pp.
Volume 3 1972 (0-471-25879-2) 401 pp.
Volume 4 1974 (0-471-25881-4) 660 pp.
Volume 5 1975 (0-471-25882-2) 864 pp.
Volume 6 1977 (0-471-25873-3) 765 pp.
Volume 7 1979 (0-471-02918-1) 487 pp.
Volume 8 1980 (0-471-04834-8) 602 pp.
Volume 9 1981 (0-471-05631-6) 596 pp.
Volume 10 1982 (0-471-86636-9) 528 pp.
Volume 11 1984 (0-471-88628-9) 669 pp.
Volume 12 1986 (0-471-83469-6) 643 pp.
Volume 13 1988 (0-471-63007-1) 472 pp.
Volume 14 1989 (0-471-50400-9) 386 pp.
Volume 15 1990 (0-471-52113-2) 432 pp.
Volume 16 1992 (0-471-52721-1) 435 pp.
Volume 17 1994 (0-471-00074-4) 464 pp.
Volume 18 1999 (0-471-24477-5) 518 pp.
Volume 19 1999 (0-471-32709-3) 504 pp.
Volume 20 2000 (0-471-36999-3) 552 pp.
Volume 21 2002 (0-471-21393-4) 608 pp.
Volume 22 2006 (0-471-68243-8) 504 pp.

Aus dem Klappentext

This highly successful series has provided generations of professional chemists with a comprehensive, up-to-date look at the reagent literature. The format of the series continues with its concise descriptions, good structural formulas, and selected examples of application, providing references to new reagents as well as to reagents included in previous volumes.

This volume covers synthetic literature from 2003 to 2004.

CONTENTS:

Reagents

Author Index

Subject Index

Auszug. © Genehmigter Nachdruck. Alle Rechte vorbehalten.

Fiesers' Reagents for Organic Synthesis, Volume 23, Fiesers' Reagents for Organic Synthesis

John Wiley & Sons

Chapter One

Oxidation. 3,4-Dihydroxy-1-alkenes which can be prepared from 2-alken-4-ols via reaction with singlet oxygen undergo oxidation, initially to 1-alken-3-on-4-ols (with 1 equiv. each of acetamido-TEMPO and TsOH) and then the unsaturated diketones (2.5 equiv. reagents).

Acetic anhydride. 20, 1, 21, 1; 22, 1

Acetylation.1 Hydroxy groups of sugars are protected by reaction with [Ac.sub.2]O in the presence of 4A-molecular sieves. Conditions permit survival of acid-labile groups. Selectivity for primary alcohols is shown.

Benzannulation. Substituted dibenzofurans are readily synthesized by the following method.

Acetonitrile(cyclopentadienyl)triphenylphosphineruthenium hexafluorophosphate.

3-Hydroxyalkanitriles. The cationic Ru complex, NaP[F.sub.6], and an amine base form a cooperative catalyst that can activate MeCN in nucleophilic addition to aldehydes (11 examples, 77-93%).

Acetonyltriphenylphosphonium bromide. 21, 1; 22, 1

Acetalization. With the reagent as catalyst carbonyl compounds are converted into acetals (and thioacetals). A polymer form can also be used.

Acetylacetonato(dicarbonyl)rhodium. 21, 1; 22, 2-4

Hydroformylation. High anti-selectivivity is achieved in the formation of [alpha]-alkyl aldols from allylic o-diphenylphosphinylbenzoates. The reaction of unsaturated esters can give rise to 1,3- or 1,4-dicarbonyl products, depending on reaction conditions. The tris(2,4-di-t-butylphenyl)phosphate ligand seems important because very low conversion is observed with [(PhO).sub.3]P.

Hydroformylation followed by aldol cyclization with an internal enolborate is stereo-selective. It is also possible to form arylhydrazones or indoles from arylhydrazines and alkenes (via homologation of the alkenes).

Silylative cyclization. Allenynes with suitably separated unsaturated linkages undergo cyclization on a catalyzed hydrosilylation. 5- and 6-membered carbocycles and heterocycles are readily synthesized from allenyl aldehydes.

4-Alkynones. 1-Alkynes add to enones (MVK) to produce 4-alkynones. Alkynyl(hydrido)rhodium species are involved. Enones are weaker ligands than alkynes for Rh, therefore it requires excess of enones to drive the reaction.

Acetylacetonato(diolefin)rhodium. 21, 2; 22, 4

Reductive acylation. Arylboronic acids react with cyclobutanones in the presence of (acac)Rh[(ethene).sub.2] to give aryl ketones.

Conjugate additions. Reductive arylation of enones and alkenyl sulfones by ArB[(OH).sub.2] is catalyzed by (acac)Rh[(ethene).sub.2]. Both transformations are subjected to asymmetric induction in the presence of chiral ligands.

Acetyl chloride. 22, 5

Desilylation. TBS ethers are rapidly cleaved with catalytic amount of AcCl in dry MeOH, typically at room temperature.

Acetylation. The normal trend for acetylation of alcohols (prim.>sec.) is reversed when Si[O.sub.2] is present. Thus 1,5-hexanediol gives 5-acetoxyhexanol in 60% yield.

Acetyl hypofluorite.

Fluorination. Silyl ketene acetals react with AcOF at -45 to give [alpha]-fluoroalkanoic esters.

N-Acylbenzotriazoles. 22,

Preparations. In addition to the conventional use of SO[Cl.sub.2] and BtH, direct reaction of RCOOH with BtS[O.sub.3]Me also gives these reagents.

Acylations. Acyl transfer to primary and secondary alkyl nitriles to give -keto nitriles is carried out with these reagents, usually at room temperature (t-BuOK/DMSO). Similarly, -keto sulfones are prepared (BuLi is used to deprotonate the sulfones).

Highly regioselective C-acylation of at a b-position of pyrroles and indoles using the title reagents is promoted by Ti[Cl.sub.4].

Carboxylic acid derivatives. RCOBt are convenient precursors of hydroxamic acids, thiol esters, and oxazolines/thiazolines.

[alpha]-Diketones. Symmetrical [alpha]-diketones are produced when RCOBt are exposed to Sm[I.sub.2].

Acyl fluorides. 22, 5

Reductive acylation. Reduction of lactones with Dibal-H followed by kinetic trapping of the hemiacetals with RCOF avoids ring opening. The reaction on esters works well when X = F but not with X = Cl.

N-Acyl(methanesulfonamides).

N-Acylation. Amines form amides on heating the mixture with the reagents (via decomposition of the salts). A primary amino group reacts more readily and N-acylation takes preference to O-acylation in amino alcohols.

Alkoxydiphenylphosphines.

Esters and phenyl ethers. Together with a quinone (2,6-dimethylbenzoquinone the best) [Ph.sub.2]POR forms an adduct which is capable of esterifying carboxylic acids and phenols. Acidic compounds (not ordinary alcohols) react through proton transfer to generate adequate nucleophiles.

2-Alkoxymethylsulfonylbenzothiazoles.

Vinyl ethers. These reagents are useful for Julia olefination.

Alkylaluminum chlorides. 22, 7-8

[2 + 2]Cycloaddition. Cyclobutanes are obtained when silyl enol ethers and substituted alkenes are brought together in the presence of EtAl[Cl.sub.2].

Hydroxybenzylation. Baylis-Hillman-type reaction of [alpha],-unsaturated lactones is promoted by [Et.sub.2]AlI.

Alkylation reactions. [Et.sub.3][Al.sub.2][Cl.sub.3] promotes alkyl chloroformates to transfer their alkyl groups to alkenes.

N-Alkylation and ITLITL-allylation of imines are performed in tandem with organoaluminum halides and allyltributylstannane.

Rearrangement. Ketene-N, O-acetals isomerize to the more stable amides by an O->C alkyl migration process when they are treated with MeAl[Cl.sub.2].

Dehydration. Alkenylsilane synthesis initiated by addition of [Me.sub.3]SiC[H.sub.2]Li to carbonyl compounds (best in [Et.sub.3]N) is completed by heating the adducts directly with [Et.sub.2]AlCl at 150 as to avoid desilylation.

Alkyliminotris(dimethylamino)phosphoranes.

Michael reaction. These RN = P[(N[Me.sub.2]).sub.3] and a few other nonionic bases are useful catalysts for the Michael reaction of -keto esters in water.

1-Alkyl-3-methylimidazolium salts. 20, 70; 21, 85; 22, 88-91

Common transformations. There are too numerous routine reactions being repeated in ionic liquids, just mentioning them is impractical. Therefore a more critical selection is presented.

Interconversion of alkyl halides and alcohols are more facile in ionic liquids, due to apparent increase in the nucleophilicity of water. Halide ions from the salts enter the TsOH-catalyzed substitution.

Formation of t-butyl alkyl ethers from t-BuOH and ROH without an acid catalyst is described. Heating the mixture with 1-decyl-3-methylimidazolium tetrafluoroborate accomplishes the task. Glycosylation that employs trichloroacetimidates as glycosyl donors proceeds well at room temperature in an ionic liquid....