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 . . . . . . . . . . . . . 153 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 Springer-V&g Berlin HeidelbergN ewYork London Paris Tokyo 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 wiii, however, always be pleased to receive suggestions and suppsementa~ information. Papers are accepted for “Topics in Current Chemistry” in English. 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) Thii work is subject to copyright. 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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 Table of Contents of Volume 133 Small Ring Compounds in Organic Synthesis I Introduction A. de Meijere Strain and Reactivity: Partners for Selective Synthesis B. M. Trost The Application of Cyclobutane Derivatives in Organic Synthesis H. N. C. Wong, K.-L. Lau and K.-F. Tam Synthesis and Synthetic Applications of 1-Metallo-l-Selenocyclopropanes and -cyclobutanes and Related 1-Metallo-l-silylcyclopropanes Alain Krief Facult~s Universitairesd e Namur, l~partment de Chimie Rue de Bru×elles6 1, 5000 Namur, Belgium Table of Contents 1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2 Syntheses of 1-Functionalized-Metallo Small Ring Compounds . . . . . . . 9 2.1 Syntheses of Functionalized (1-Seleno-, 1-Silyl-, 1-Vinyl-)Cyclopropyl- lithiums . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 2.1.1 Attempted Synthesis Using Hydrogen-Metal Exchange . . . . . 12 2.1.2 Synthesis Implying Heteroatom-Metal Exchange . . . . . . . . 13 2.1.2.1 Synthesis of 1-Selenocyclopropyllithiums by Selenium- Metal-Exchange from Selenoacetals of Cyclopropanones 13 2.1.2.2 Synthesis of 1-Vinylcyclopropyllithiums by Selenium-Metal Exchange from 1-Seleno- 1-vinylcyclopropanes . . . . . . 14 2.1.2.3 Synthesis of 1-Silylcyclopropyllithiums . . . . . . . . . 15 2.2 Synthesis of Functionalized 1-Selenocyclobutylmetals. . . . . . . . . 20 2.3 Synthesis of 1,1Bis-(Seleno)cyclopropanes . . . . . . . . . . . . . . 21 2.3.1 Syntheses Which Involve the Construction of the Cyclopropane Ring 21 2.3.1.1 By Metallation Reaction . . . . . . . . . . . . . . . 21 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 3.1 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 4.1 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, 135 © Springer-Ver|ag, Berlin Heidelberg 1987 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 . . . . . . . . . . . . . . . . . . 41 4.2.1. Synthesis of 1-Hetero-l-vinylcyclopropanes by Dehydration Reactions . . . . . . . . . . . . . . . . . . . . . . . . . 41 4.2.1.1 Synthesis of 1-Seleno-l-vinylcyclopropanes . . . . . . . 41 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 D e r i v a t i v e s . . . 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 . . . . . . . . . . . . . . . . . 61 4.5.1.1 From 13-Cyclopropylselenides and an Acid . . . . . . . . 61 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 containinga selenenyl moiety have been transformed to selenium free derivatives such as alkylidene cyclopropanes, vinyl cyclopropanes, allylidene cyelopropanes, cyclobutanones and ~-sityl cyctopropyllithiums. The latter compounds have been used as starting material for the 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 cyclo~ butanes, vinyl cyclobutanes, oxaspirohexanes and cyetopentanones. Synthesis and SyntheticA pplications 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 R1 R1 I RSeM + X-~;-R 2 = R S e - C - R 2 H, H, X = h o t o g e n , o s u i f o n a t e . . , Scheme I leq 0 3 a A" CH 2 =CHOct RSe CH2CH2Oct _~or1~IMCPB~ o \2ecII~CP B A 11 .oM b or MnO~Kc yc = R;e-CH2C H2Oct NuCHz-CHO2 ct 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 13,14) and under more drastic conditions (Scheme 2 b). 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) R1 ~P R1 L~ R1 I 3 auLi - I 2 I PhSeC-R ,- hSe-C-IR - P h L i * B u - C - R 2 /2 THF L i 1 Bu R3 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, lo,12,15) (Scheme 4b). The selenenyl moiety in 3 0 • R 1 OH ta B u L l ;- S e - (THFr7 8"C.0,5h) R 2 R4 R1 / I RSe-C-SeR -]M~3s~° R4 0 R 4 SeR nC,, - Lo-Z: , RSeSnCI41 ~ R ° - C - - C - C - R , "1 H5 Scheme 4