Small ring compounds in organic synthesis / Vol. 2

161 Pages·1987·7.882 MB·English

by  A de Meijere

Table of Contents
Synthesis and Synthetic Applications of
1-Metallo-l-Selenocyclopropanes and -cyclobutanes and
Related 1-Metallo-l-Silylcyclopropanes
A. Kricf . . . . . . . . . . . . . . . . . . . . . . .
Cyclopropenes and Methylenecyclopropanes as
Multiftmctional Reagents in Transition Metal Catalyzed
Reactions
P. Binger and H. M. Bfich . . . . . . . . . . . . . . . 77
Author Index Volumes 101-135 . . . . . . . . . . . . . 351
SmallR ing Compounds
in OrganicS ynthesisII
Editor: A. de Meijere
With ~~ut~bu~tion~b y
I?B inger,H . M. Biich, A. Krief
With 5 Figuresa nd 11T ables
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ISBN 3-540-16662-9 Sponger-Verlag Berlin Heidelberg New York
ISBN O-387-16662-9 Springer-Verlag New York Heidelberg Berlin
Library of Congress Cataloging-in-PubiCcation Data
(Revised for vol. 2)
Small ring compounds in organic synthesis.
{Topics in cnrrent chemistry ; 133-l
Vol. 2 edited by A. de Meijere; with contriibutibns by P. Binger, II. M. Biich, A. Krief.
Includes index.
1. Chemistry, Organic-Synthesis-Addresses, essays, lectures. 2. Ring formation
(Chemistry)-Addresses, essays, iectnres. I. Meijere, A. de. II. Series: Topics in current
chemistry ; 133, etc.
QDl.F58 vol. 133, etc. [QD262] 540 s [547’.2] 861271
ISBN O-387-16307-7 (U.S. : v. 1)
ISBN O-387-16662-9 (U.S. : Y. 2)
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Editorial Board
Prof. Dr. Michael J. S. Dewar Department of Chemistry, The University of Texas
Austin, TX 78712, USA
Prof. Dr. Jack L?. Dwtitz Laborutorium tilr Organiscbe Cbemie der
Eidgeniissischen Hochschuie
UniversititsstraDe 6/8, CH-8006 Zthich
Prof. Dr. Klaus Hafner Institut Fur Organische Chemie der TH
PetersenstraDe 15. D-6100 Darmstadt
Prof. Dr. Edgar ffdbronmer Physikalisch-Chemisches Institut der Universimt
Klinge1bergstraC-e 80, CK-4000 Base1
Prof. Dr. S/r6 lib Department of Chemistry, Tohoku University,
Sendai, Japan 980
Prof. Dr. Jean-Marie Lehn Institut de Chimie, Universite de Strasbourg, 1, rue
BIaise Pas&, B. P. 2 296/R8, F-67008 Strasbourg-Cedex
Prof. Dr. Kurt Niedenzv University of Kentucky, Coilege of Arts and Sciences
Department of Chemistry, Lexington, KY 40506, USA
Prof. Dr. Kenneth N. Rarmomd Department of Chemistry, University of California,
Berkeley, California 94720, USA
Prof. Dr. Charles W, Rees Hofmann professor of Organic Chemistry, Department
of Chemistry, Imperial College of Science and Technology,
South Kensington, London SW7 2AY. England
Prof. Dr. Klaus Sch@er Institut fur Physikalische Chemie der Universitat
Im Neuenhelmer Feld 253, D-6900 Heidelberg I
Prof. Dr. Ritz Wgtfe Institut fur Organ&he Chemie und Biwhemie
der Universit&t, Gerhard-Domagk-Str. 1,
D-5300 Bonn 1
Prof. Dr. Georg Wittig Institut filr Organ&he Chemie der Universiffit
Im Neuenheimer Feld 270, D-6900 Heidelberg 1
of Table stnetnoC of emuloV 331
Small Ring sdnuopmoC I Synthesis in Organic
Introduction
A. de Meijere
Strain and Reactivity: Partners for Selective Synthesis
B. M. Trost
The Application of Cyclobutane Derivatives in Organic
sisehtnyS
H. N. C. Wong, K.-L. Lau and K.-F. Tam
Synthesis dna Synthetic Applications
of 1-Metallo-l-Selenocyclopropanes dna -cyclobutanes dna
Related 1-Metallo-l-silylcyclopropanes
Alain Krief
seriatisrevinU s~tlucaF l~partment Namur, de ed eimihC euR ed selle×urB ,16 0005 Namur, muigleB
Table of Contents
1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2 Syntheses of 1-Functionalized-Metallo Small Ring Compounds ....... 9
1.2 Syntheses of Functionalized (1-Seleno-, 1-Silyl-, 1-Vinyl-)Cyclopropyl-
lithiums . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.1 Attempted Synthesis Using Hydrogen-Metal Exchange ..... 21
2.1.2 Synthesis Implying Heteroatom-Metal Exchange ........ 31
2.1.2.1 Synthesis of 1-Selenocyclopropyllithiums by Selenium-
Metal-Exchange from Selenoacetals of Cyclopropanones 31
2.1.2.2 Synthesis of 1-Vinylcyclopropyllithiums by Selenium-Metal
Exchange from 1-Seleno- 1-vinylcyclopropanes ...... 41
2.1.2.3 Synthesis of 1-Silylcyclopropyllithiums ......... 51
2.2 Synthesis of Functionalized 1-Selenocyclobutylmetals ......... 20
2.3 Synthesis of 1,1Bis-(Seleno)cyclopropanes . . . . . . . . . . . . . . 12
2.3.1 Syntheses Which Involtvhee Construction of the Cyclopropane Ring 12
2.3.1.1 By Metallation Reaction . . . . . . . . . . . . . . . 12
2.3.1.2 By Selenium-Metal Exchange . . . . . . . . . . . . . 22
2.3.2 Syntheses Which Involve the Reaction of Selenols on a Pre-built
Functionalized Cyclopropane Ring .......... .... 24
3 Reactivity of 1-Functionalized-l-Metaiio. Small Ring Compounds ...... 24
1.3 Alkylation with Alkyl and Allyl Halides, Epoxides, and Trimethyl silyl
Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.2 Hydroxy Alkylation with Carbonyl Compounds . . . . . . . . . . . 26
4 Reactions Involving the Removal of the Selenenyl or the Silyl Moiety from
~z-Seleno and 0t-Silyl Cyclopropane and Cyclolmtane Derivatives ....... 29
1.4 Syntheses of Alkylidene cyclopropanes and Alkylidene Cyclobutanes.. 30
4.1.1 Syntheses ofAlkylidene cyclopropanes and Alkylidene cyclobutanes
by Formal Elimination of a Selenenyl Moiety and a Hydrogen 30
Topics in Current Chemistry. Vol, 531
© Heidelberg Berlin Springer-Ver|ag, 7891
Alain Krief
4.1.1.1 Syntheses of Alkylidene cyclopropanes from 1-Alkyl-1-
Selenocyclopropanes . . . . . . . . . . . . . . . . . 30
4.1.1.2 Syntheses ofAlkylidene cyclobutanes from 1-Alkyl-l-seleno-
cyclobutanes . . . . . . . . . . . . . . . . . . . . 33
4.1.2 Syntheses ofAlkylidene cyclopropanes and cyclobutanes by Formal
Elimination of a Hydroxyl Group and a Heteroatomic Moiety 35
4.1.2.1 Syntheses of Alkylidene cyclopropanes . . . . . . . . . 35
4.1.2.2 Syntheses of Alkylidene cyclobutanes . . . . . . . . . . 40
4.2 Syntheses of Vinylcyclopropanes . . . . . . . . . . . . . . . . . . 14
4.2.1. Synthesis of 1-Hetero-l-vinylcyclopropanes by Dehydration
Reactions . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.2.1.1 Synthesis of 1-Seleno-l-vinylcyclopropanes ....... 14
4.2.1.2 Synthesis of 1-Silyl-l-vinylcyclopropanes ........ 42
4.2.2 Synthesis of 1-Hetero-l-vinylcyclopropanes by Elimination of Two
Heteroatomic Moieties . . . . . . . . . . . . . . . . . . . 44
4.2.3 Miscellaneous Syntheses of l-Hetero-l-vinylcyclopropanes .... 49
4.3 Synthetic Transformations Involving l-Heterosubstituted-l-vinylcyclo-
propanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.3.1 Reactions Involving 1-Seleno-l-vinylcyclopropanes ....... 50
4.3.1.1 Synthesis of 1-Functionalized-l-vinylcyclopropanes Via
1-Lithio- 1-Vinylcyclopropanes . . . . . . . . . . . . . 50
4.3.t.2 Syntheses of Functionalized Alkylidene cyclopropanes . . 50
4.3.1.3 Synthesis of Carbonyl Compounds . . . . . . . . . . . 53
4.3.2 Reactions Involving 1-Silyl-l-vinylcyclopropanes ........ 53
4.3.2.1 Synthesis Involving 1-Seleno- 1-vinylcyclopropanes .... 53
4.3.2.2 Thermal Rearrangement to cyclopentane Derivatives... 53
4.4 Diels-Alder Reactions Involving Allylidene cyclopropanes ...... 55
4.5 Syntheses of Carbonyl Compounds by Ring-Enlargement Reactions . . 59
4.5.1 Syntheses of Cyclobutanones . . . . . . . . . . . . . . . . . 16
4.5.1.1 From 13-Cyclopropylselenides and an Acid ........ 16
4.5.1.2 From l-Seleno-l-vinylcyclopropanes and an Acid .... 63
4.5.1.3 From i~-Selenocyclopropanols . . . . . . . . . . . . . 64
4.5.2 Syntheses of Cyclopentanones . . . . . . . . . . . . . . . . 64
4.5.2.1 From Oxaspirohexanes Derived from 13-Hydroxy-
cyclobutylselenides and from 13-Selenocyclobutanols • • • 64
4.5.2.2 Directly from 13-Selenocyclobutanols . . . . . . . . . . 69
4.5.2.3 From 13-Selenoxy cyclobutanols Via 13-Seleno cyclo-
pentanones . . . . . . . . . . . . . . . . . . . . . 69
4.5.2.4 Conclusion . . . . . . . . . . . . . . . . . . . . . 70
5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Synthesis and Synthetic Applications
Among the a-heterosubstituted cyclopropylmetals a-selenocyclopropyllithiums represent some of
the most valuable synthetic intermediates. They are quantitatively prepared from selenoacetals of
cyclopropanones and butyllithiums, are thermally stable at ~ --78 ° for several hours and are parti-
cularly nucleophilic especially towards carbonyl compounds. The cyclopropyl derivatives containing a
selenenyl moiety have been transformed to selenium free derivatives such as alkylidene cyclopropanes,
vinyl cyclopropanes, allylidene cyelopropanes, cyclobutanones and ~-sityl cyctopropyllithiums. The
latter compounds havbee en used as starting material fotrh e synthesis of alkylidene cyclopropanes and
cyclopentenyl derivatives. ~-Seleno cyclobutyllithiums, which are available in two steps from cyclo-
butanones, also permit the synthesis of various selenium free homologues such as alkylidene ~olcyc
butanes, vinyl cyclobutanes, oxaspirohexanes and cyetopentanones.

sisehtnyS dna citehtnyS snoitacilppA
1 Background
The presence of a selenenyl moiety in organic molecules confers on them unique
properties 1-12). The selenium atom in selenides is particularly nucleophilic towards,
for example, alkyl halides and halogens 1,2) (Scheme 1); it is oxidizable leading
1 R 1 R
RSeM + X-~;-R 2 =RSe-C-R I 2
H, H,
X = hotogen, o suifonate..,
Scheme I
3 0 leq
a A" 2 CH =CHOct
RSe CH2CH2Oct _~or1~IMCPB~
o
11 .oM
C~IIce2\ PB A 2HC-e;R tcO2HC 2HC-zHCuN tcO
b ro K~OnM =
cyc
o
NuM= Na],NaOH,NaN3,PhSM
Scheme 2
selectively to selenoxides 3-9'H'~2) under mild conditions (Scheme 2a) or to
selenones with excess of oxidant )41,31 and under more drastic conditions (Scheme b). 2
The selenium atom is also electrophilic: selenides react with alkyllithiums and lead to
novel selenides and novel organometallics by cleavage of the original C--Se bond
(Scheme 3) 7-9,12)
1R P~ 1R L~ 1R
I 3 auLi - I 2 I
PhSeC-R ,- hSe-C-IR -PhLi * Bu-C-R 2
/2 FHT L i 1
Bu 3 R ~I 3
Scheme 3
Finally the selenenyl moiety is perfectly able to stabilize a carbanion 7--9,12)
(Scheme 4a) or a carbenium ion ,9 )51,21,ol (Scheme 4b). The selenenyl moiety in
3 0 • 1 R OH
ta BuLl ;- Se-
rFHT( )h5,0.C"87
2 R R4
1 / R
I
RSe-C-SeR
°~s3~M]- 4 R 0 4 R SeR
- Lo-Z:
nC,, , RSeSnCI41 ~R°-C--C-C-R ,
1" 5H
Scheme 4