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Book Review The Chemistry of Organophosphorus Compounds. Vol. 2 Phosphine Oxides Sulphides Selenides and Tellurides. (Series The Chemistry of Functional Groups. Series editor S. Patai.) Edited by F. R

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butadienelhafnocene (s-cis-7c)precipitated as orange crystals in approximately 50 % yield.[’] Photolysis of s-cis-7c
(10 % solution in toluene) quantitatively yields the s-trans-7c
isomer, which in turn isomerizes to the more stable s-cis-7c
above 0°C [s-trans-7c+s-cis-7c: AG* (300 K) = 22.6
0.5 kcalmol-1].[81
Our experiments show that C-H bonds in simple organic
substrates can be easily activated by using a combination of
a main group element and a transition metal. Since many
complexes with combinations of moieties containing d-block
metals and main group elements are now easily accessible,rg1
we shall devote attention to these “heterodimetallic” compounds as stoichiometric reagents or catalysts for the activation of organic substrates.
Received: March 23, 1993 [Z 5952 IE]
German version: Angew. Chem. 1993. 105, 1216
See for example: F. Antwi-Nsiah. M. Cowie. Orgunomerollics 1992, 11,
3157; Y. Ishii. Y. Ishino, T. Aoki, M. Hidai. J. Am. Chem. Soc. 1992, 114,
5429; V. Dufand, J. Thivolle-Cdzat, J. M. Basset, R. Mathieu, J. Jand. J.
Waissermann. 0rganometulht.s 1991. 10, 4005; J. Schwank. Stud. Surf Sci.
Curd. 1991,64,225; Chem. Abstr. 1991, 115.240877~;M. Ichikawa, Polyhedron 1988, 7,2351 ; A. Fukuokd, M. Ichikawa, J. A. Hriljac, D. F. Shriver,
Inor‘q. Chem. 1987,26,3643; S. Sato, B. Chaudret, D. Gervais. R. Poilblanc.
N o w J Chim. 1981, 5 , 597; C. P. Horwitz, D . F. Shriver. Adv. Orgunomer.
C h e m 1984. 23, 219; E. L. Muetterties. J. Stein, Chem. Rev. 1979, 79. 479;
E. L. Muetterties, T. N. Rhodin, E. Band,C. F. Brucker. W. R. Pretzer, ibid.
1979. 79, 91. and references therein, cf.: J. Hine, Ace. Chem. Res. 1978,
il. 1 .
G. Erker, J. Wicher, K. Engel, F. Rosenfeldt, W. Dietrich, C. Kriiger, J. Am.
C h m . Sot.. 1980, 102. 6344; H. Yasuda, Y. Kajihara, K. Mashima. K.
Nagasuna. K. Lee, A. Ndkamura. Orgcmomerallics 1982. 1.388; G. Erker.
K. Engel. C. Sarter in “Organometalk Synthesis” Yo/. 3 (Eds.: R. B. King,
J. J. Eisch), Elsevier, Amsterdam, 1986, p. 32.
G. Erker. K . Engel, U. Dorf, J. L. Atwood, W. E. Hunter, Angew. Chem.
1982. Y4.915; Angew. Chem. In[. Ed. Engl. 1982,Zi. 914; G. Erker, U. Dorf,
R. Benn. R:D. Reinhardt, J. L. Petersen. J. Am. Chem. Soc. 1984, 106,
7649; G. Erker, T. Miihlenbernd, R. Benn, A. Rufinska, Organomeial/ics
1986, 5 . 402; G. Erker. R. Lecht, R. Schlund, K . Angermund, C. Kriiger,
Angeic. Chem. 1987,99,708; Angew. Chem. lnt. Ed. Engl. 1987,26,666; G.
Erker. R. Lecht. J. L. Petersen, H . Bonnemann, OrgunometuNics 1987, 6,
1962. G. Erker, R. Lecht, Y.-H. Tsay. C. Kriiger, Chem. Ber. 1987, 120,
1763. Review: G. Erker, Angew. Chem. 1989, 101,411; Angew. Chem. Inr.
Ed. Engl. 1989, 28, 397.
[4] Crystal structure analysis of 6a: Crystal size 0.10 x 0.26 x 0.54 mm, monoclinic, space group P2,, a =10.665(5), b =7.819(1), c = 13.429(4) A, /l
109.87(3)”, V = 1053.2(4) A3, Z = 2, pCslrd
= 1.342 gem-', F(000) = 448,
p(Mo,,) = 5.27 cm-’, Siemens-P4-diffrdctometer, T = 295 K. graphite2642 meamonochromated Mo,. (2. = 0.71073 .&). 20-scan 2-50.0
sured reflections of which 2278 were unique and 1868 observed at F > 4.0
a(F).237 independent parameters refined, Siemens SHELXTL PLUS program, direct methods, R = 0.0393. R, = 0.0415. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information
mbH, D-76344 Eggenstein-Leopoldshafen, on quoting the depository number CSD-57168, the names of the authors, and the journal citation.
[5] G. Erker, K. Engel. J. L. Atwood. W E. Hunter, Angew. Chem. 1983, 95.
506. Angew. Chem. lnr. Ed. Engl. 1983.22.494. See also: E. G. Hoffmann.
R. Kallweit, G. Schroth, K . Seevogel, W. Stemptle, G. Wilke. J. Orgunomer.
Chem. 1975, 97, 183; G. Erker, K. Berg, K. Angermund. C. Kriiger,
Orgunometullic.y 1987. 6.2620. and references therein.
161 U. Dorf, K. Engel, G. Erker, Angew. Chem. 1982, 94, 916. Angew. Chem.
Inr. Ed. Eng/. 1982,2i, 914; J. S. McDermott. J. F. White, G . M. Whitesides,
J. Am. Chem. Soc. 1976. 98, 6521, 6529; T. M. Miller, G. M. Whitesides,
Orgunomrru//its 1986, 5, 1473.
[7] For conventional syntheses of 1-(9-BBN)-substituted 1,3-butddiene and
other boryl-substituted olefins see: R. Koster, A. Bussmann, G. Schroth.
Liehigs Ann. Chem. 1975, 2130; G. M. Clark, K. G. Hancock, G. Zweifel.
J. Am. Chem. Soc. 1971, 93, 1308; G. Zweifel, G. M. Clark, N. L. Polston,
ihid. 1971, 93, 3395; R. Koster, Pure Appl. Chem. 1977. 49. 765; D . A.
Singleton, J. P. Martinez, G. M. Ndip, J. Org. Chem. 1992. 57. 5768; T. E.
Cole. R. Quintanilla, ibid. 1992, 57, 5768; T. E. Cole. R. Quintanilbd. ihid.
1992, 57, 7366; R. H. Wallace. K. K. Zong, Tetrahedron Lerr. 1992. 33,
6941; I. Rivera, J. C. Colberg. J. A. Soderquist, ibid. 1992, 33. 6919: N.
Noiret, Y. Youssofi, B. Carboni, M. Vaultier, J. Chem. Soc. Chem. Commun.
1992, 1105; H. C. Brown, U. R. Khire, U. S. Racherla. Tetrahedron Leir.
1993.34, 15; R. Koster, G. Seidel, K . Wdgner, B. Wrackrneyer. Chem. Ber.
1993, 126, 305. R. Koster, G. Seidel, K. Wagner. B. Wrdckmeyer. ihid. 1993,
126. 319, and references therein. Review. R. Koster in “OrgunohorVerhindungen I” (Merhoden Org. Chem. (Houben-We.y/) 41h Ed. 1952-),
Band 13/3a, 1982, p. 206ff.
[8] G. Erker. J. Wicher, K . Engel, C. Kriiger, Chem. Ber. 1982. 115.3300; G.
Erker, K. Engel. C . Kriiger. A.-P. Chiang, &id. 1982, 115, 331 1 ; U. Dorf.
K. Engel, G. Erker. OrgunomeruNics 1983, 2,462; G. Erker. C . Kriiger. G.
Miiller, Adv. Organomel. Chem. 1985, 24, 1; G. Erker, T. Miihlenbernd. A.
Rufinska, R. Benn, Chem. Ber. 1987. i20. 507.
191 G. Erker, R. Zwettler, C . Kriiger, R. Noe, S. Werner, J Am. Chem. Soc.
1990, 112, 9620; G. Erker, M. Albrecht, C. Kriiger, S. Werner,
Organometal/ics 1991, 10. 3791; M. Albrecht, G. Erker, M. Nolte, C.
Kriiger, J. Orgunornet. Chem. 1992, 427, C21; G. Erker, Comments lnorg.
Chem. 1992, 13, 111; G. Erker, M. Albrecht, S. Werner, M. Nolte. C.
Kriiger, Chem. Ber. 1992,125,1953; G. Erker, M. Albrecht, C. Kriiger, S.
Werner, P. Binger, F. Langhauser, OrganomeruNics 1992. 11, 3517; G. Erker, M. Albrecht, C. Kriiger, S. Werner, J. Am. Chem. SOC.1992, 114, 8531;
G. Erker, R. Noe, C. Kriiger, S. Werner, Orgunomerallies 1992, 11. 4174.
Book Reviews
The Chemistry of OrganophosphorusCompounds.Vol. 2: Phosphine Oxides, Sulphides, Selenides and Tellurides. (Series :
The Chemistry of Functional Groups. Series editor: S .
Patai.) Edited by E R . Hartley. Wiley, Chichester, 1992.
XVI, 647 pp., hardcover E 3 60.00.-ISBN 0-471-93 056-3
The comments of this reviewer (Angew. Chem. 1992, 104,
109; Angew. Chem. Znt. Ed. Engl. 1991,30,1046) on the first
volume of the four-volume series “The Chemistry of Organophosphorus Compounds”, which appeared in 1990, are also
applicable to this second volume. No major handbook on
Chem l n t Ed Engl 1993, 32, No 8
mhH D-6945i Wernheim I993
. -
0570 0833/93/0808-1215$ 1000+ 2SjO
organophosphorus chemistry has been published for a long
time, and this new series is therefore very welcome. Many
developments have occurred in this field during the last
twenty years, and it is important that they should be covered
in a work of this kind.
The area covered by Volume 2, namely phosphine oxides,
sulfides, selenides, and tellurides, is certainly one of the most
important parts of organophosphorus chemistry. However,
some related compound classes are not covered in this volume, for example the important class of phosphine imides of
the type XYZP(=NR), where X, Y, and Z are hydrocarbon
groups, which can be regarded as formally related to phosphine oxides. In reviewing this volume it would have been
helpful to be given a detailed plan for the complete series.
Such an overall plan should at least be provided with Volumes 3 and 4 that are still to be published.
Returning to the present volume, there is no doubt that it
offers an up-to-date and (almost) complete description of
a very important area of organophosphorus chemistry,
which is treated in detail in more than 600 pages. The editor
has aimed at emphasizing important recent developments
rather than attempting an encyclopedic coverage. The subjects covered by the eight chapters are: structure and bonding in tertiary phosphine chalcogenides (D. G . Gilheaney);
structure and stereochemistry of secondary and tertiary phosphine chalcogenides (M. J. Gallagher); electrochemistry of
organophosphorus(v) compounds (K. V. S. Santhanamhere the subject matter is by no means limited to phosphine
chalcogenides); photochemistry of phosphine chalcogenides
(M. Dankowski); spectroscopy of phosphine chalcogenides
(G. Davidson); methods for preparing phosphine chalcogenides (A. K. Bhattacharya and N. K. Roy); chemical properties and reactions of phosphine chalcogenides (R. S. Edmundson); coordination chemistry of phosphine chalcogenides, and analytical and catalytic applications (T. S. Lobana).
The volume gives a comprehensive and up-to-date survey of
the field of phosphine chalcogenides. Numerous references to
the original literature are included, extending to very recent
work. Each chapter begins with an introduction giving the
background to the topic, and continues up to the most recent
developments. As well as giving an overall picture, the chapters indicate where more detailed information can be found.
The chapter on the spectroscopy of phosphine chalcogenides is especially welcome, and covers UV/visible, vibrational, and N M R spectroscopy. It would have been desirable
to have a chapter like this in Volume 1, especially with regard
to N M R studies, and one hopes that Volumes 3 and 4 will
also include these aspects.
The sequence of the chapters does not seem entirely appropriate; in particular, Chapters 6 and 7 (on preparative methods, chemical properties, and reactions) should, in my view,
have been placed at the beginning of the book. The term
“phosphine chalcogenides” is not interpreted in the same
way by all the authors: in some chapters it is taken to mean
only tertiary phosphine chalcogenides, whereas in others it
includes both secondary and tertiary phosphine chalcogenides. There is also a lack of uniformity in the formula
diagrams, with the phosphorus-chalcogen double bonds
shown too long in some cases, giving an unattractive appearance. Inconsistencies are also evident in the literature coverage. For example, there is some confusion with regard to
citing the Russian literature, which is especially important in
organophosphorus chemistry: sometimes only the English
translation is cited, whereas in other (rarer) cases only the
Russian original is cited; it would have been better always to
give both. Where citations in unusual o r obscure journals are
given, they are not always accompanied by the Chemical
VCH Verlagsgesell.~chaf!m h H , D-69451 Wc+fherm,1993
Abstracts reference. Unfortunately some authors’ names have
become garbled ; sometimes the same name appears several
times with different spellings, and so on. Moreover, it seems
that the authors essentially interpret phosphine chalcogenides as compounds with only one phosphorus atom; I
found no obvious mention of related compounds with two or
more phosphine chalcogenide centers (for example, linked
together through heteroatoms). Some other related compound types also appear to be absent. Thus, in cases where
one needs to make an exhaustive search it is necessary to
consult other sources. The volume includes a detailed author
index and a (less comprehensive) subject index, both of which
are useful.
Now that two of the four volumes have appeared, it can be
said that the overall impression is still favorable, and the remaining two volumes are awaited with interest.
Reinhard Schmutzkr
Institut fur Anorganische und Analytische Chemie
der Technischen Universitiit Braunschweig (FRG)
Enantioselective Synthesis. Natural Products from Chiral Terpenes. By Tse-Lok Ho. Wiley, Chichester, 1992. XII,
324 pp., hardcover E 56.00.-ISBN 0-471 -54 819-7.
The development of methods for the synthesis of enantiomers (rather than racemates) is a very important area of
research. A new book on this subject will therefore interest
many, but expectations will be high. This book deals with an
important sub-domain, namely natural product synthesis
starting from simple, chiral natural building blocks having
high enantiopurity-~-the chiral pool, in the present case terpenes. The essential point is, of course, that the chirality and the
enantiopurity of the building block are transferred, wherever
feasible, into the synthetic target compound.
In the preface it is stated that “... there is an apparent lack
of a comprehensive summary of terpene-based syntheses” and
one sentence later that ‘<...consequently it seems worthwhile
to collate and discuss the important contributions in this
area”. Now it is clearly impossible to treat this huge area in
this single, relatively thin volume. A selection must have been
made, but it is up to the reader to find out what the selection
is. This is the only really serious criticism I have. Nowhere
does the author define the actual scope of the book.
The author has restricted himself mainly to multi-step syntheses, which are described and discussed, but with very little
background information, and to starting materials that are
almost exclusively monoterpenes (citronellene, citronellol,
linalool, oxidized derivatives; limonene; menthone, piperitone, perilla aldehyde and related compounds; pulegone;
carvone; carenes and thujone; pinenes ; camphor and congeners; other terpenes).
The chapter on the camphors, for example, contains about
50 references, whereas the review article on the same subject
by Money-which
is cited--contains 240 primary references, many of which contain multiple citations. The difference is due to the fact that the latter review covers not only
the types of syntheses dealt with in the book, but also all the
classical chemistry that has made the multiple functionalizations of the camphors possible. This chemistry is only mentioned in passing in the book, and without real help as to
how to get access to it (“ ... a thorough knowledge of its
(camphor’s) chemistry is most critical [Money, 19851”).
It is more difficult to judge how comprehensive the coverage of the syntheses is. We again selected the camphors and
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