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New Methods for the Synthesis of Organozinc and Organocopper Reagents

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Claudia Piazza New Methods for the Synthesis of Organozinc and Organocopper Reagents München 2002 Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München New Methods for the Synthesis of Organozinc and Organocopper Reagents Claudia Piazza aus Treviso, Italien München, 2002 Erklärung Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung vom 29. Januar 1998 von Professor Dr. Paul Knochel betreut. Ehrenwörtliche Versicherung Diese Dissertation wurde selbständig, ohne unerlaubte Hilfe erarbeitet. München, am 30. Oktober 2002 Claudia Piazza Dissertation eingereicht am 30. Oktober 2002 1. Gutachter: Prof. Dr. Paul Knochel 2. Gutachter: Prof. Dr. em. Wolfgang Steglich Mündliche Prüfung am 4. Dezember 2002 Table of Contents Introduction 1 Overview 2 1.1 Organozinc reagents 2 1.2 Uncatalysed reactions of zinc organometallics 5 1.2.1 Aminomethylation 5 1.2.2 Fragmentation of homoallylic zinc alcoholates 6 1.2.3 Generation of benzylic zinc reagents 9 1.3 Transition metal catalysed reactions of zinc organometallics 10 1.4 Organocopper reagents 11 1.4.1 Vinylic organocuprates 13 2 Objectivies 16 Results and Discussion 1 Aminomethylation of Functionalized Organozinc Reagents and Grignard Reagents 19 1.1 Summary 23 2 Preparation of Benzylic Zinc Reagents via a Fragmentation Reaction 24 2.1 Summary 27 3 Preparation of Allylic Zinc Reagents via a Cyclization-Fragmentation Reaction 28 3.1 Attempted synthesis of functionalized allylic zinc reagents via a cyclization-fragmentation reaction 34 3.2 Summary 35 4 Preparation of Highly Functionalized Organocuprates via Halogen-Copper Exchange 36 4.1 Higher order cyanocuprates 36 4.2 Non-transferable ligands 36 4.3 Functionalized aryl cyanocuprates 38 4.4 Screening of other non-transferable groups 39 4.5 Neopentyl and neophyl group as non-transferable ligands 41 4.6 Halogen-copper exchange on functionalized arylic compounds 42 4.6.1 Reactions of lithium dineopentylcuprate 43 4.6.2 Aldehydes and ketones: reactions of neophylcuprate 46 4.7 Regioselective functionalization of polyiodinated arylic substrates 50 4.8 The role of copper cyanide 54 4.9 Substitution reactions with functionalized mixed cuprates 54 4.10 Summary 56 5 Iodine-Copper Exchange on Vinylic Substrates 57 5.1 Summary 60 6 Halogen-Copper Exchange on Heterocycles 61 6.1 Summary 65 7 Summary and Outlook 66 Experimental Section 1 General Conditions 72 2 Typical Procedures (TP) 75 TP 1 Typical procedure for the aminomethylation of functionalized organozinc and Grignard reagents 75 TP 2 Typical procedure for palladium-catalyzed deprotection of allylamines 75 TP 3 Typical procedure for the preparation of benzylic alcohols via a fragmentation reaction 75 TP 4 Typical procedure for the generation of homoallylic zinc reagents via a cyclization-fragmentation reaction 76 TP 5 Typical procedure for the halogen-copper exchange on arylic substrates 76 TP 6 Typical procedure for the iodine-copper exchange on ethyl (2Z)-3-iodo-3-phenylpropenoate 77 TP 7 Typical procedure for the bromine-copper exchange on N,N-diallyl-2-bromo-3-methyl-butenamide 77 TP 8 Typical procedure for the iodine-copper exchange on imidazole derivatives 78 3 Synthesis of Organozinc and Organocopper Reagents 79 4 Aminomethylation of Functionalized Organozinc Reagents and Grignard Reagent Using Immonium Trifluoroacetates 82 5 Preparation of Benzylic Zinc Reagents via a Fragmentation Reaction 91 6 Preparation of Allylic Zinc Reagents via a Cyclization-Fragmentation Reaction 101 7 Preparation of Highly Functionalized Organocuprates via Halogen-Copper Exchange 116 8 Iodine-Copper Exchange on Vinylic Substrates 133 9 Halogen-Copper Exchange on Heterocycles 140 10 Abbreviations 151 Introduction 2 1 Overview Organozinc and organocopper reagents are an indispensable part of the synthetic chemist’s knowledge. Nowadays, almost every synthesis of natural product has at least one step which involves the use of this kind of compounds. Therefore, there is a constant need for the development of new methods for a straightforward and efficient preparation of zinc and copper organometallics. In this work the attention was focused on a new approach for the preparation of benzylic and allylic organozincs, which are among the most reactive zinc species. Even if diorganozincs and organozinc halides display only moderate reactivity toward most organic electrophiles, the scope and synthetic application of these species were greatly extended when it was found that they can accommodate a wide range of functional groups. An important C-C bond forming reaction for the construction of nitrogen-containing molecules is the addition of carbon nucleophiles to iminium intermediates. For this reason, the use of zinc reagents with these highly reactive elctrophiles for the synthesis of functionalised amines will also be described. The vast majority of experimental protocols for the preparation of organocopper complexes involve the transmetalation process from other organometallic species. This places a limitation in the functional groups that can be present in the molecule, depending on the precursor of choice. The search for a method that avoids the transmetalation step, allowing the preparation of organocoppers bearing any kind of functionalities by direct halogen-copper exchange reaction, was considered to be of a remarkable synthetic utility and was therefore attempted. 1.1 Organozinc reagents With the synthesis of diethylzinc in 1849, E. Frankland lay the foundation stone for modern organometallic chemistry.1 However, organomagnesium2 and organolithium3 reagents were the first reagents to dominate this branch of organic chemistry. Although almost ignored for more than 100 years after their discovery, organozinc compounds are today one of the most useful class of organometallic reagents, due to their easy preparation and higher functional group 1 a) Frankland, E. Liebigs Ann. Chem. 1848-49, 71, 171. b) Frankland, E. J. Chem. Soc. 1848-49, 2, 263. 2 Grignard, V. Compt. Rend. 1900, 130, 1322. 3 a) Schlenk, W.; Holtz, J. Chem. Ber. 1917, 50, 262. b) Ziegler, K.; Colonius, H. Liebigs Ann. Chem. 1930, 479, 135. 3 compatibility in comparison with organolithium and Grignard reagents. Furthermore, their excellent reactivity in the presence of the appropriate catalyst makes them a very powerful tool for natural product synthesis, as illustrated in the preparation of prostaglandin intermediates 1 and 24 (Scheme 1). O O O OPiv O 1) IZnCH2OPiv CuCN 2 LiCl TBDMSO TMSCl, THF TBDMSO Pent TBDMSO 2) 1N HCl Pent Pent TBDMSO TBDMSO TBDMSO 83 % 1 O O 1) IZn CO Me 2 CO2Me TBDMSO TBDMSO CuCN 2 LiCl Pent Pent TMSCl, THF TBDMSO TBDMSO 2) L-Selectride 58 % 3) aq. HF, CH3CN 2 Scheme 1 There are three main classes of organozinc compounds:5 organozinc halides (RZnX), diorganozincs (R2Zn) and lithium or magnesium zincates. Organozinc halides are readily available by the direct insertion of zinc dust into organic halides6 (Scheme 2). 4 a) Miyaji, K.; Ohara, Y.; Miyauchi, Y.; Tsuruda, T.; Arai, K. Tetrahedron Lett. 1993, 34, 5597. b) Yoshino, T.; Okamoto, S.; Sato, F. J. Org. Chem. 1991, 56, 3205. c) Koga, M.; Fujii, T.; Tanaka, T. Tetrahedron 1995, 51, 5529. 5 Knochel, P.; Jones, P. Organozinc Reagents. A Practical Approach, Oxford University Press, 1999. 6 a) Berk, S. C.; Yeh, M. C. P.; Jeong, N.; Knochel, P. Organometallics 1990, 9, 3053; b) Berger, S.; Langer, F.; Lutz, C.; Knochel, P.; Mobley, A.; Reddy, C. K. Angew. Chem. 1997, 109, 1603; Angew. Chem. Int. Ed. 1997, 36, 1496. c) Rottändler, M.; Knochel, P. Tetrahedron Lett. 1997, 38, 1749. d) Zhu, L.; Wehmeyer, R. M.; Rieke, R. D. J. Org. Chem. 1991, 56, 1445. 4 Zn RX RZnX X = I, Br THF O NHBoc IZn CO Bn 2 ZnI Scheme 2 Diorganozinc reagents require different methods of preparation, like iodine-zinc and boron-zinc exchange.7 These methods are applicable to the formation of primary and secondary diorganozinc species8 (Scheme 3). Et2Zn 1) Et2BH 1 1 1 R -(CH2)2-I R (CH2)2 Zn R CuX cat. 2 2) Et2Zn Zn AcO Zn TIPSO 2 2 Scheme 3 Remarkably, by using i-Pr2Zn, configurationally defined secondary dialkylzinc reagents have been prepared7c (Scheme 4). OBn 1) Et BH (3 equiv) OBn 1) CuCN 2LiCl OBn 2 H H 50 °C, 16 h -78 °C, 30 min Ph 2 1 Ph Ph 2) i-Pr Zn (3 equiv) 2) 1-bromo-1-hexyne (5 equiv) 2 3 Zni-Pr 25 °C, 5 h -55 °C, 2 d Bu dr(1,2) = 93 : 7 dr(1,2) > 99 : 1 overall yield 47 % Scheme 4 7 a) Langer, F.; Waas, J.; Knochel, P Tetrahedron Lett. 1993, 34, 5261. b) Langer, F.; Schwink, L.; Devasagayaraj, A.; Chavant, P.-Y.; Knochel, P. J. Org. Chem. 1996, 61, 8229. c) Boudier, A.; Hupe, E.; Knochel, P. Angew. Chem. 2000, 112, 2396; Angew. Chem. Int. Ed. 2000, 39, 2294. 8 a) Schwink, L.; Knochel, P. Tetrahedron Lett. 1994, 35, 9007. b) Devasagayaraj, A.; Schwink, L.; Knochel, P. J. Org. Chem. 1995, 60, 3311. 5 Diorganozincs display enhanced chemical reactivity compared to alkylzinc halides, but even more reactive are lithium or magnesium zincates, which are readily prepared by transmetalation reactions from the corresponding magnesium or lithium reagents and are well suited to halogen- zinc exchange reactions9 (Scheme 5). R2Zn + RM R3ZnM ZnCl2 + 3RM Br Br Br R3ZnLi R'Br Pd (0) Br Zn(L) R' Scheme 5 1.2 Uncatalysed reactions of zinc organometallics 1.2.1 Aminomethylation In contrast with organolithium and Grignard reagents, organozincs have a relatively covalent carbon-metal bond, resulting in their more moderate reactivity than that of organometallics containing a more polar carbon-metal bond. Only reactive classes of organozinc reagents like allylic zinc halides10 and zinc enolates11 efficiently undergo additions to carbonyl compounds. On the other hand, a few classes of highly reactive electrophilic reagents directly react with zinc organometallics, among them immonium salts. Iminium salts are important intermediates in organic synthesis12 and aminomethylation is a transformation which has been performed with various immonium salts13 or iminium salt precursors.14 The reaction of these intermediates with functionalised organozinc reagents was first reported by Saidi,15 who performed a three component aminoalkylation of aldehydes promoted by lithium perchlorate.
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  • Synthesis and Properties of Diorganomagnesium Compounds

    Synthesis and Properties of Diorganomagnesium Compounds

    University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 12-1967 Synthesis and Properties of Diorganomagnesium Compounds Conrad William Kamienski University of Tennessee - Knoxville Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Chemistry Commons Recommended Citation Kamienski, Conrad William, "Synthesis and Properties of Diorganomagnesium Compounds. " PhD diss., University of Tennessee, 1967. https://trace.tennessee.edu/utk_graddiss/3077 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Conrad William Kamienski entitled "Synthesis and Properties of Diorganomagnesium Compounds." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Jerome F. Eastham, Major Professor We have read this dissertation and recommend its acceptance: Bruce M. Anderson, George K. Schwitzer, David A. Shirley Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) Novemb er 27, 1967 To the Graduate Council: I am submitting herewith a dissertation written by Conrad Wiliiam Kamienski entitled "Synthesis and Properties of Diorgano­ magnesium Compounds." I recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a maj or in Chemistry .