Organic Chemistry

221 Pages·1985·12.938 MB·English

by  Kurt P. Meurer, Fritz Vögtle (auth.)

scipoT ni
Current Chemistry
Managing Editor: E .L Boschke
Editorial Board: M.J.S. Dewar .J .D Dunitz
721
.K Hafner .E Heilbronner .S Ito J-M. Lehn
~I Niedenzu .K .N Raymond .C .W Rees
.F VSgtle .G Wittig
.K R Meurer and .F Vbgtle
Helical Molecules in Organic Chemistry
.K .G Heumann
Isotopic Separation nI Systems with Crown
srehtE and Cryptands
.T Mukaiyama and ,M inrasA
Chiral Pyrrolidine Diamlnes sa Efficient
Ligands in Asymmetric Synthesis
.H .J Keller and Z .G Soos
Solid refsnarT-egrahC Complexes of
Phenazines
Springer-Verlag Berlin Heidelberg NewYork Tokyo
721 Topics ni Current Chemistry
der Fortschritte nehcsimehC gnuhcsroF
Managing Editor: E L. Boschke
cinagrO yrtsimehC
hti.W Contributions by
.M Asami, .K G. Heumann, .J .H Keller,
.K .P Meurer, .T Mukaiyama, .Z G. ,sooS
E eltg6V
With 831 Figures and 64 Tables
Springer-Verlag
Berlin Heidelberg New York oykoT
5891
This series presents critical reviews of the present position and future trends
in modern chemical research. It is addressed to all research and industrial
chemists who wish to keep abreast of advances in their subject.
As a rule, contributions are specially commissioned. The editors and publishers
will, however, always be pleased to receive suggestions and supplementary
information. Papers are accepted for "Topics in Current Chemistry" in
English.
ISBN 3-540-15088-9 Springer-Verlag Berlin Heidelberg New York Tokyo
ISBN 0-387-15088-9 Springer-Verlag New York Heidelberg Berlin Tokyo
Library of Congress Cataloging in Publication Data. Main entry under title:
Organic chemistry.
(Topics in current chemistry = Fortschritte der chemischen Forschung; )721
Bibliography: p. Includes index.
l. Chemistry, Organic -- Addresses, essays, lectures.
I. Asami, M. If. Series: Topics in current chemistry; 127.
QDI.F58 vo1.127 [QD255] 540s[547] 84-26879
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012345-0203/2512
Managing Editor:
Dr. hcirdeirF L. Boschke
Springer-Verlag, Postfach 501 280, D-6900 Heidelberg 1
Editorial Board:
Prof. Dr. Michael J. S. Dewar Department of Chemistry, The University of Texas
Austin, TX ,21787 USA
Prof. Dr. Jack .D Dunitz Laboratorium for Organische der Chemic
Hochschule Eidgen6ssischen
Universit~tsstra~ Ziirich 6/8, CH-8006
Prof. Dr. glaus Hafner Institut der Chemie f~r Organi~che TH
eBartsnesreteP .51 Darmstadt D-6100
Prof. Dr. Edgar Heilbronner sebcsimebC-hcsilakisyhP Institut der Universitgt
¢3IartsgreblegnilK .08 CH-4000 lesaB
Prof. Dr. Sh6 h6 Department of Chemistry, Tohoku University,
Scndai, Japan 089
Prof. Dr. Jean-Marie Lehn Institut de de Chimie, Universit6 Strasbourg, ,1 rue
esialB Pascal, .B .P Z 296/R8, 80076-F Strasbourg-Ccdex
Prof. Dr. Kurt Niedenzu University of Kentucky, College of Arts and secneicS
Department of Chemistry, Lexington, KY ,60504 USA
Prof. Dr. N. Kenneth Raymond Department of Chemistry, University of California,
,yelekreB California ,02749 USA
Prof. Dr. Charles .W Rees Hofmann Professor of Organic Chemistry, Department
of Imperial Chemistry, egelloC of ecneicS Technology, and
South Kensington, London 7WS 2AY, England
Prof. Dr. Fritz V6gtle lnstitut fiir Organische Chemic und eimebcoiB
der Universitit, Gerhard-Domagk-Str. I,
0035-D Bonn I
Prof. Dr. Georg Wittig lnstitut ffir der Organische Chemic tt~tisrevinU
Im Neuenheimer Feld Heidelberg 270, D-6900 1
Table of Contents
Helical Molecules in Organic Chemistry
K. P. Meurer, F. V6gtle . . . . . . . . . . . . . . . .
Isotopic Separation in Systems with Crown Ethers and Cryp-
tands
K. G: Heumann . . . . . . . . . . . . . . . . . . . 77
Chiral Pyrrolidine Diamines as Efficient Ligands
in Asymmetric Synthesis
T. Mukaiyama, M. Asami . . . . . . . . . . . . . . . 331
Solid Charge-Transfer Complexes of Phenazines
H. J. Keller, Z. G. Soos . . . . . . . . . . . . . . . . 961
Author Index Volumes 101-127 . . . . . . . . . . . . . 217
Helical Molecules ni Organic Chemistry
Kurt P. Menrer 1 and Fritz 2 VOgtle
1 BAYER AG, Wissenschaftliches Hauptlaboratorium 5090 Leverkusen, FRG
2 Institut fiir Organische Chemie und Biochemie der Universit~it Bonn, Gerhard-Domagk-StraBe ,1
D-5300 Bonn ,1 FRG
Table of Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1 Screw Structures in Chemistry . . . . . . . . . . . . . . . . . . . 3
1.2 Definition of a Helix in Chemistry . . . . . . . . . . . . . . . . . 10
1.3 Molecular Propellers . . . . . . . . . . . . . . . . . . . . . . . 14
2 Aiiphatic and Aiicyclic Helices . . . . . . . . . . . . . . . . . . . . . . 19
2.1 Atrop Isomers . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.2 Spiro Isomers . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.3 Twist Isomers . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.4 Helical Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.4.1 Aliphatically Clamped Alkenes . . . . . . . . . . . . . . . . 25
2.4.2 Distorted Alkenes . . . . . . . . . . . . . . . . . . . . . 27
2.4.3 Helical Aralkenes . . . . . . . . . . . . . . . . . . . . . . 28
2.4.4 Helical Oligoalkenes . . . . . . . . . . . . . . . . . . . . 30
2.4.5 Helical Allenes . . . . . . . . . . . . . . . . . . . . . . . 31
2.4.6 Topological Aliphatic Helices . . . . . . . . . . . . . . . . 32
3 Aromatic Helices: Helicenes . . . . . . . . . . . . . . . . . . . . . 32
3.1 Carbohelicenes . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.2 Heterohelicenes . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.3 Double Helicenes . . . . . . . . . . . . . . . . . . . . . . . . 47
3.4 Helicenes Containing Cyclophane Units . . . . . . . . . . . . . . 49
3.5 Helical Metallocenes . . . . . . . . . . . . . . . . . . . . . . . . 51
3.6 Bihelicenyls . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.7 Circulenes, Dehydrohelicenes . . . . . . . . . . . . . . . . . . . 52
4 Araliphatic Helices: Helicenophanes and Arenicenes . . . . . . . . . . . 53
4.1 Helicenophanes . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.2 Araliphatic Propellers . . . . . . . . . . . . . . . . . . . . . . 58
4.3 Arenicenes: Aliphatically Bridged Oligophenyl Assemblies . . . . . . . 59
Ktrt P. Meurer and Fritz V6gtle
4.3.1 Pentaphenylenicenes . . . . . . . . . . . . . . . . . . . . 59
4.3.2 Tetraphenylenicenes . . . . . . . . . . . . . . . . . . . . 60
4.3.3 Triphenylenicenes . . . . . . . . . . . . . . . . . . . . . 62
4.4 Helical [2.2]Metacyci~phanes . . . . . . . . . . . . . . . . . . . 66
5 Conclusions and Outlook . . . . . . . . . . . . . . . . . . . . . . . 68
6 Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . 70
7 Referene~ s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
lacileH seluceloM ni cinagrO yrtsimehC
1 Introduction
1.1 Screw Structures in Chemistry
Screw structures or helices (helix: Greek ~Xt~ = winding, convolution, spiral) are
encountered in various variations in nature and technique. Propeller-shaped, helical
structures play an important role in architecture, physics, astronomy and biology.
Screw-shaped macromolecular skeletons of nucleic acids, proteins and potysaccharides
are important structural elements in biochemistry. Their helix turns often are stabilized
through hydrogen bonds, metal cations, disulfide linkages and hydrophobic inter-
actions.
• -Amylose was the first helix postulated for a natural macromolecule. In solution
it contains approx, six glucose units per turn and is stabilized through hydrogen
bridges connecting the three hydroxy groups. Normally, the amylose "host molecule"
contains on the average, one "guest" water molecule per glucose unit. The cavities
of the helix are just large enough to take up approx, one 21 molecule per helix turn la, .)a2
The enclosed iodine guest causes the characteristic intense blue color. The helical
cavities of amylose, having a diameter of approx. 450-700 pm (6-helix and 7 helix,
resp.) )b2 also enclose stilbenes and other compounds of appropriate size. The 6-helix
forms the most stable amylose and can harbor benzene as well as aliphatic compounds
in its cavities .)b2
One of the most important natural compounds with a helical structure is deoxy-
ribonucleic acid (DNA). It was studied by Watson and Crick )3 based on the X-ray
analysis of Franklin and Gossling .)4 Two right-handed polynucleotide chains are
wound around a central axis. The sugar phosphate chains form an outer screw line,
whereas the purine and pyrimidine bases are projecting inside. Their ring planes are
1
,, , /0-.. g"~ 0
""" .O 0 ~/~-" O'J~ 0
o
lo o o
o o
L; /--o
.giF .1 Structure )deifilpmis( of the esolyma-t0 helix ni(
s t )noitulos
/
Kurt P. Meurer and Fritz V6gtle
p~O:G"C'o p
pD" A ....... T--'O p
D --T ....... A D
'PD~"'- ~'o:.c G ....... C "-'~D P
~o "p
p. DXA',T- D.p
pO'-----C
....... G --'-'O.p
D C ....... G D
PD--A ........ O T'~-;_. "P
P'o:j;~o ~"
b A-DNA B-DNA Z-DNA
Fig. 2. a Classical DNA structure, b structure of A-, B- and Z-DNA Lc( Saenger, )>b5
parallel to each other and approx, perpendicular to the central axis. Hydrogen bonds
between complementary bases allow the legendary "double-helix structure", which