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Organometallic Chemistry — for Organic Synthesis Abbreviations in Chemical Structures

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Organometallic Chemistry — for organic synthesis Abbreviations in Chemical Structures Me CH - methyl Bz PhC(O)- benzoyl Contents 3 Et MeCH2- ethyl Boc t-BuOCO tert-butoxycarbonyl 1. Main group organometallic chemistry Pr EtCH2- n-propyl Ts p-TolSO 2- p-toluenesulfonyl 1-1. Preparations Bu PrCH2- n-butyl Ms MeSO2- methanesulfonyl 1-2. Reactions Pent BuCH2- n-pentyl Tf CF3SO2- trifluoromethanesulfonyl Hex PentCH - n-hexyl TMS Me Si- trimethylsilyl 2. Reactions of organic molecules and transition-metal complexes 2 3 i-Pr Me2CH- isopropyl TES Et3Si- triethylsilyl 3. Reactions catalyzed by transition-metal complexes i-Bu i-PrCH- isobutyl TBS t-BuMe2Si- tert-butyldimethylsilyl 3-1. Hydrogenation s-Bu EtMeCH- sec-butyl 3-2. Cross-coupling and related reactions t-Bu Me3C- tert-butyl c-Pent c-C H - cyclopentyl 3-3. Olefin metathesis 5 9 t-Am EtMe2C- tert-amyl 3-4. Homogeneous metal catalysts in chemical industry Cy (c-Hex) c-C6H11- cyclohexyl Ph C6H5- phenyl pin -OCMe2CMe2O- pinacolate Bn PhCH2- benzyl cat 1,2-C6H4O2 catecholate Books o-Tol 2-MeC6H4- 2-methylphenyl 1. Comprehensive Organometallic Chemistry III m-Tol 3-MeC6H4- 3-methylphenyl R any C substituents eds. by D. M. P. Mingos and R. H. Crabtree, Elsevier, Oxford, 2007. p-Anis 4-MeOC6H4- 4-methoxyphenyl Ar any aromatic substituents (https://www.sciencedirect.com/science/referenceworks/9780080450476) PMB p-AnisCH2- 4-methoxybenzyl X any halogen and related leaving group Xyl 5-Me-m-Tol - 3,5-dimethylphenyl M any metal substituents 2. 第５版 実験化学講座 有機化合物の合成 VI 金属を用いる有機合成 Mes 2,4,6-Me3C6H2- mesityl 日本化学会 編, 丸善, 2004. (ISBN4-621-07317-6) 1-(a-)Np 1-C10H7- 1-naphtyl TMEDA Me2NCH2CH2NMe2 2-(b-)Np 2-C H - 2-naphtyl HMPA (Me N) P=O 3. 有機金属化学 10 7 2 3 Ac MeC(O)- acetyl 山本明夫, 東京化学同人, 2015. (ISBN978-4-8079-0857-8) 4. Organotransition Metal Chemistry: From Bonding to Catalysis Periodic Table J. F. Hartwig, University Science Books, Sausalito, 2010. (ISBN978-1-8913-8953-5, 日本語訳あり) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 5. Organic Syntheses H He http://www.orgsyn.org/Default.aspx Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba Ln Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Lanthanoids (Ln) La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu – 1 – 1. Main group organometallic chemistry Half lives of organolithium compounds in ethereal solvents (min) 1-1. Preparations –40°C –20°C 0°C 20°C 35°C n-BuLi 9180 1860 (0) What is organometallic compounds? in Et2O s-BuLi 1187 139 “Organometallic compounds” means the compounds containing one or more carbon–metal t-BuLi 483 61 complex (C–M) covalent bonds. n-BuLi 1039 107 Features and properties in THF s-BuLi 78 • The organometallic compound has one or more C–M bonds t-BuLi 338 42 • It behaves as a carbanion (carbon nucleophiles) to react with electrophilic compounds P. St anet t y, J. Org. Chem., 62, 1514 (1997). • Reactivity of the C–M bond is greatly affected by electronegativity (c) of the metal atom. Mechanism Li, Mg etc. (small c) Unstable to water and oxygen Mg0 – • R X Mg+ • R X R• •MgX R MgX Not easy to handle in air Too reactive. • The generation of Grignard reagent starts from the electron transfer from metal to organic B, Si, Sn etc. (large c) Relatively stable to water and oxygen halide. Possible to be purifies with extraction and/or chromatography • The reaction proceeds through the radical species, which must be kept low concentration to avoid its homocoupling. (1) Preparation from organic halides and metal (direct method) • In the case of lithium, LiX is generated in the second step. The radical species, R•, reacted Some main group organometals are prepared from the corresponding organic halides with Li atom in place of •MgX. through the reaction with metal elemental substance. This method offers the most fundamental preparation of organolithium and magnesium compounds. (a) Lithium arenide – • R X M = Li etc. (alkali metal) Li + Li+ R Li THF R X + 2 M R M + MX lithium naphthalenide (LN) M = Mg etc. (alkaline earth metal) • Lithium give an electron to the LUMO of naphthalene, forming a radical anion, lithium R X + M R MX (X = I, Br, Cl) naphthalenide (LN). • The redox potential of naphthalenide is higher than that of the metal, but LN is soluble in Notice THF (or related solvent). The high solubility of naphthalenide much facilitates the electron • The reactions are greatly affected by shape of the metal (dispersion, granular, or ingot). transfer to organic halides. • Reactivity of lithium metal is affected by sodium impurity (<1%). The impurity facilitates the • Use of LN allows preparation of organolithiums at low temperature. The mild condition reaction. leads to restriction of the undesired Wurtz reaction. • Lithium or magnesium can be activated with a small piece of iodine or 1,2-dibromoethane. • A catalytic amount of naphthalene is enough for efficient production of organolithiums. • Some organozincs, e.g. Reformatsky and Simmons–Smith reagents, can be obtained from • Arenes below are also usable for the generation of anion radical in place of naphthalene. the reaction of the halide and zinc metal. Zinc–copper couple (alloy) is frequently NMe2 employed for the preparation. t-Bu t-Bu • Optimal solvent depends on the halide as well as the metal. Therefore, the solvent must be carefully chosen for each combination. Et2O and THF is favorable for the preparation DMAN DBB of Grignard reagent and aryllithium. The preparation of alkyllithium is ordinarily carried out Application in hydrocarbon solvent. O Li OH • The organic halide should be carefully and slowly (0.1–3 h) added to the metal suspension OEt OLi OEt OEt DBB (10%) PhCMe H2O to avoid Wurtz reaction. Li Me Cl Me OEt Ph OEt THF, –20°C OEt Ph CO2Et L. Duhamel, Tetrahedron Lett., 39, 8975 (1998). – 2 – (b) Rieke metal Et2O 1. CO2 cat. naphthalene R X Br + Bu Li Li + Bu Br CO H + 2 MXn + n Na or K "M" R M 2. H3O – n NaX or KX (pKa = 50) (pKa = 43) Rieke metal 84% R. D. Rieke, Acc. Chem. Res., 10, 301 (1977); Tetrahedron 53, 1925 (1997). H. Gilman, J. Am. Chem. Soc., 62, 2327 (1940). • Metal halides, MXn, are reduced with sodium arenide to fine metal particles, which are THF 1. PhCHO OH named Rieke metal. I + EtMgBr MgBr rt + • Rieke metal is more reactive than common metal powder. N N 2. H3O N Ph • Various organometals, e.g. Mg, Zn, In, Ca, Cu etc., can be prepared under mild conditions 91% through the reaction of organic halide with Rieke metal. N. Furukawa, Tetrahedron Lett., 28, 5845 (1987). (c) Knochel’s organozinc preparation Turbo Grignard Reagent (i-PrMgCl•LiCl) cat. i-Pr Cl + Mg + LiCl i-Pr MgCl•LiCl THF, rt, 12 h BrCH2CH2Br (5%) R I ZnI•LiCl Br Zn Me3SiCl (1%) Br Br Br t-BuCHO + i-Pr MgCl•LiCl (R = CO Et) cat. OH LiCl 2 R R THF, –50°C, 2 h Br CuCN•2LiCl Br Br Br MgCl•LiCl t-Bu P. Knoc hel, Angew. Chem. Int. Ed., 45, 6040 (2006). 89% P. Knochel, Angew. Chem. Int. Ed., 43, 3333 (2004). • The addition of LiCl remarkably enhance the reactivity of purchasable zinc powder. • Turbo Grignard reagent, i-PrMgCl•LiCl, is more reactive for the X–Mg exchange reaction • The zinc is activated by catalytic 1,2-dibromoethane and TMSCl in the presence of LiCl. than common Grignard reagents. With the reagent, the desired organomagnesiums can The resulting Zn•LiCl readily reacts with various iodo-, bromoarenes, and bromoalkanes. be prepared from the corresponding bromoarenes at low temperature (< 0°C). • This method is applicable for the generation of various functionalized organometal species, • Turbo Grignard reagent is generated from the reaction of i-PrCl and magnesium turnings because organizinc compounds are commonly inert to various functional groups, e.g. in the presence of anhydrous LiCl. ketone, ester, and nitrile. • This method is applicable for the generation of various Grignard reagents bearing various (2) Metal–halogen (M–X) exchange reaction reactive functional groups, such as carboxylate and nitrile. M = Li, MgX etc. R X + R' M R M + R' X (3) Metal–metal (M–M’) exchange reaction (transmetalation) X = I, Br, SeR, TeR etc. (a) Exchange reaction between organometallic compound and metal halide • In the mixture of an organohalide (R–X) and organometal (R’–M), the halogen in R–X is MX = ZnCl , R SnCl, R SiCl, R B(OMe), etc. readily replaced by the metal R’–M to give another organometal R–M. R M’ + MX R MX + M’X n 2 3 3 2 n n–1 M’ = Li, MgX • The metal–halogen exchange reaction is more convenient for preparing the aryl and alkenyl- lithiums in small scale than the direct method. • This reaction is the most reliable method for preparing less reactive organometals, Zn, Al, • In this reaction, R’–M and R–M are in equilibrium. The equilibrium is affected by the Sn, Si, B etc. Organolithium or magnesium is mostly employed as the starting material. thermal stability of each carbanion. The reaction proceeds to the right, when R’–H is larger • This reaction is also in equilibrium. Nevertheless, the desired organometals are obtained in pKa than R–H.
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    Chem 341 • Organic Chemistry I Lecture Summary 29 • November 02, 2007 Chapter 10 - Alkyl Halides Preparation of Organometallic Compounds - Grignard reagents Alkyl halides are good electrophiles. We will examine their reactivity in nucleophilic substitution in detail in the next chapter. Another useful property of alkyl halides as that reducing metals can insert between the C-X bond to prepare a C-metal bond. This drastically alters the reactivity as the metal is less electronegative than carbon. Thus, the reactivity of the carbon is reversed from being an electrophile to being a nucleophile. Grignard reagents are formed from the insertion of Mg metal into the C-X bond. These reagents are very reactive as bases and electrophiles and are extremely sensitive to any source of proton (water, ROH, RNH2, etc). This can be useful if one wants to reduce an alkyl halide to an alkane. It is also a useful method of introducing hydrogen isotopes, such as deuterium, by reaction of the Grignard reagent with heavy water (D stands for Deuterium, the isotope of hydrogen 2H). Grignard reagents can be prepared from a variety of different kinds of organohalides (eg. Alkyl halides, vinyl halides, etc.). One important reaction of Grignard reagents is their ability to add to carbonyl compounds (C=O double bonds). You will study this in detail next semester. δ− δ+ δ+ Br δ− Mg Br D Mg D2O O reactivity of OH carbon reversed R H then H+ R Preparation of Organometallic Compounds - Gilman reagents Lithium metal reacts with organohalides in a simlar fashion as magnesium. Organolithium reagents are very basic and are often used to deprotonated compounds that are not very acidic.
  • REVIEW Methyl Complexes of the Transition Metals

    REVIEW Methyl Complexes of the Transition Metals

    REVIEW Methyl Complexes of the Transition Metals Jesús Campos,[b] Joaquín López-Serrano,[a] Riccardo Peloso,[a] and Ernesto Carmona*[a] Dedicated to Prof. Pierre Braunstein in recognition of his contributions to inorganic and organometallic chemistry [a] Title(s), Initial(s), Surname(s) of Author(s) including Corresponding Author(s) Department Institution Address 1 E-mail: [b] Title(s), Initial(s), Surname(s) of Author(s) Department Institution Address 2 Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate)) REVIEW Abstract: Organometallic chemistry can be considered as a wide focusing in the last 5 years. It begins with a brief description of area of knowledge that combines concepts of classic organic synthetic methods, followed by a selection of recently reported chemistry, i.e. based essentially on carbon, with molecular inorganic complexes with terminal and bridging methyl ligands from the chemistry, especially with coordination compounds. Transition metal groups 3 to 11 of the periodic table. A specific section is methyl complexes probably represent the simplest and most dedicated to methyl-bridged species with three-centre two- fundamental way to view how these two major areas of chemistry electron bonds. The review concludes highlighting relevant combine and merge into novel species with intriguing features in reactivity of the methyl group in this class of compounds. terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing Ernesto Carmona (PhD degree, University M—CH3 fragments.