Organocatalysis Mediated by (Thio)urea Derivatives

Chemistry - A European Journal - Tập 12 Số 21 - Trang 5418-5427 - 2006
Stephen J. Connon1
1Centre for Synthesis and Chemical Biology, School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland, Fax: (+353) 1‐671‐2826

Tóm tắt

Abstract

Over the last decade the potential for N,N‐dialkyl(thio)urea derivatives to serve as active metal‐free organocatalysts for a wide range of synthetically useful reactions susceptible to the influence of general acid catalysis has begun to be realised. This article charts the development of these catalysts (with emphasis on the design principles involved), from early “proof‐of‐concept” materials to contemporary active chiral (bifunctional) promoters of highly selective asymmetric transformations.

Từ khóa


Tài liệu tham khảo

 

10.1007/978-94-009-2464-2

I. Fleming Frontier Orbitals and Organic Chemical Reactions Wiley‐Interscience Chichester 1978.

It is perhaps useful to distinguish here between this mode of metal(ion)‐based catalysis which relies on Lewis acid/Lewis base interactions and those involving discrete covalently bound intermediates in which the metal often (but not always) changes oxidation state in the catalytic cycle (e.g. Pd/Ni coupling reactions Os‐mediated oxidations Ru‐catalysed olefin metathesis etc.).

 

2000, Lewis Acids In Organic Synthesis

1999, Lewis Acid Reagents

10.1002/0471721506

1999, Comprehensive Asymmetric Catalysis

Noyori R., 1994, Asymmetric Catalysis In Organic Synthesis

 

10.1021/ar000145a

10.1021/cr010289i

For recent reviews on this topic see:

10.1039/b107298f

10.1002/ange.200301732

10.1002/anie.200301732

For instructive reviews concerning general acid–base catalysis see:

10.1021/cr60280a004

10.1021/ar50108a001

10.1021/ar50150a001

10.1002/ange.200460394

10.1002/anie.200460394

For recent general reviews concerning organocatalysis see:

10.1039/b415217b

10.1002/ange.200400650

10.1002/anie.200400650

10.1021/ar040216w

10.1021/ja00337a060

 

10.1021/ja00290a067

10.1021/jo00225a021

For representative references see:

10.1021/jo00225a020

10.1021/jo00355a001

10.1021/jo00386a033

10.1021/jo00386a035

10.1016/S0040-4039(00)97402-1

For recent references concerning (asymmetric) organocatalysis mediated by diols see:

10.1021/ja037705w

10.1055/s-2003-39890

10.1002/adsc.200404065

10.1038/424146a

10.1073/pnas.0308545101

10.1021/ja044076x

10.1021/ja00019a055

10.1021/ja00053a046

10.1021/ja00225a049

10.1021/ja00179a028

10.1039/p29760000483

For further general references see:

10.1021/ar00172a005

10.1021/j100165a007

10.1021/ja00095a009

10.1021/jo00091a007

Curran D. P., 1995, Tetrahedron Lett., 36, 6647

A direct comparison between the performance of9and14was complicated by the slow decomposition of the latter at temperatures required for the Claisen rearrangement to proceed at a convenient rate.

10.1021/ol017117s

10.1002/chem.200390042

10.1021/ja00225a054

10.1021/ja00796a053

J. March Advanced Organic Chemistry 4th ed. Wiley‐Interscience New York 1992.

10.1016/S0040-4039(03)00433-7

10.1016/j.tetlet.2003.11.062

 

10.1016/S0040-4039(00)91808-2

10.1016/S0040-4039(00)60012-6

10.1021/jo00125a035

 

10.1002/poc.610030503

10.1016/0040-4039(91)80098-Q

10.1002/ange.200460059

10.1002/anie.200460059

For recent discussions proposing alternative mechanisms in non‐polar solvents see:

10.1021/ol047739o

10.1002/ange.200462462

10.1002/anie.200462462

The slow decomposition of24under the reaction conditions limits its utility in this reaction.

10.1021/cr010043d

Dessole G., 2004, Synlett, 2374

10.1021/ja961380k

10.1021/ja980139y

10.1002/(SICI)1521-3757(20000403)112:7<1336::AID-ANGE1336>3.0.CO;2-Z

10.1002/(SICI)1521-3773(20000403)39:7<1279::AID-ANIE1279>3.0.CO;2-U

10.1002/1615-4169(20010226)343:2<197::AID-ADSC197>3.0.CO;2-8

10.1021/ol005636

The opposite antipode of37 c dto those shown in Scheme 8 was used in references [40] and [42].

10.1021/ja027246j

10.1021/ja028353g

Wenzel A. G., 2003, Synlett, 1919

10.1021/ja0494398

10.1002/adsc.200505230

10.1021/ja046259p

10.1002/ange.200502277

10.1002/anie.200502277

10.1002/ange.200461814

10.1002/anie.200461814

10.1016/j.tetlet.2004.05.137

For recent reviews of bifunctional catalysis see:

Kato N., 2005, Synlett, 1491

10.1002/ange.200300635

10.1002/anie.200300635

10.1021/ja036972z

10.1021/ja044370p

10.1016/j.tetlet.2004.10.082

10.1002/ange.200500459

10.1002/anie.200500459

10.1021/ol0364531

Xu X., 2005, Chem. Eur. J., 11, 1

10.1002/ange.200461442

10.1002/anie.200461442

10.1039/B418666D

10.1021/ja0543346

10.1021/ol050431s

Lee B.‐ J., 2005, Synlett, 605

10.1002/ange.200501721

10.1002/anie.200501721

 

10.1021/ja992314w

10.1021/ja026788y

10.1021/ja046296g

10.1039/b508833j

10.1021/ja052511x

10.1021/ol051822

10.1021/ol0519137