Thesis advisor: Amir H. Hoveyda / Chapter 1. A Review of Catalytic Enantioselective Allylic Substitution (EAS) with Chiral Sulfonate Containing N-heterocyclic Carbenes (NHC). A comprehensive review of enantioselective allylic substitution reactions, which are promoted by a chiral N-heterocyclic carbene metal complex that features a unique sulfonate motif, is provided in this chapter. Reactions are classified into two categories. One class of transformations is catalyzed by a series of easily modifiable sulfonate bearing NHC-Cu complexes, with which a range of nucleophilic organometallic reagents (i.e., organozinc-, aluminum-, magnesium- and boron-based) that carry different carbon-based units are readily utilized in efficient and highly selective C-C bond forming processes. Another set of reactions exclude the use of a copper salt; catalytic amount of a sulfonate containing imidazolinium salt is capable of promoting additions of alkyl Grignard, zinc and aluminum species to easily available allylic electrophiles in a site- and enantioselective fashion. The mechanistic scenarios of both catalytic systems that account for the observed experimental data are discussed in detail. Chapter 2. Cu-Catalyzed Enantioselective Allylic Substitutions with Aryl- and Heteroarylaluminum Reagents. In this chapter, the first examples of EAS reactions of aryl- and heteroaryl-substituted dialkylaluminum reagents to a wide range of trisubstituted allylic phosphates are demonstrated through a facile and selective catalysis rendered possible by an in situ generated sulfonate containing NHC-Cu complex, delivering enantiomerically enriched olefin products that bear an all carbon quaternary stereogenic center. The requisite organometallic species are easily prepared from either the corresponding aryl- and heteroaryl halides, or through efficient and site selective deprotonation at the C-2 position of furan and thiophene; such aluminum entities are readily used in situ without the requirement of purification. Application to small molecule natural product synthesis is also carried out to illustrate the utility of the present protocol. Chapter 3. Cu-Catalyzed Enantioselective Allylic Substitutions with Alkenylaluminum Reagents. This chapter focuses on our research towards construction of enantioenriched tertiary and quaternary stereogenic centers that are substituted with two further functionalizable alkenes. The first combination of the study involves the addition of stereochemically well-defined trisubstituted alkenylaluminum reagents to disubstituted allylic phosphates; the transformation commences with a silyl-directed stereoselective hydroalumination and finishes with an enantioselective Cu-catalyzed EAS promoted by a sulfonate bearing NHC. Such reactions deliver molecules that feature silicon containing trisubstituted olefin adjacent to the tertiary stereogenic center; subsequent conversion of the versatile silicon group to a proton reveals the first set of examples that incorporate pure Z alkene in Cu-catalyzed EAS. The stereoselective and concise synthesis of naturally occurring small molecule nyasol demonstrates the utility of the above method. On a different front, Ni-catalyzed site-selective hydroalumination of terminal alkynes has opened new possibility of introducing 1,1-disubstituted olefins in Cu-catalyzed EAS in the formation of tertiary stereogenic center containing enantioenriched organic building blocks. Such catalytic hydrometallation procedure also allows efficient access to alkenylaluminums that are derived from the conventionally problematic aromatic alkynes. The importance of efficient and selective synthesis of terminal aryl-substituted alkenylaluminum species is showcased in NHC-Cu-catalyzed EAS reactions that construct all-carbon quaternary stereogenic centers; a three-step convergent synthesis of natural product bakuchiol in enantiomerically enriched form highlights the potential of the current protocol in chemical synthesis. Chapter 4 Cu-Catalyzed Enantioselective Allylic Substitutions with Alkenylboronic Acid Pinacol Ester Reagents and Applications in Natural Product Synthesis. Within this chapter, we disclose the efficient utilization of alkenylboron reagents in Cu-catalyzed EAS reactions, which lead to highly site and enantioselective formations of molecules that contain both tertiary and quaternary carbon stereogenic centers. Unlike their aluminum-based counterparts, the use of boron-based reagents allows effective delivery of sensitive organic function groups, such as a carbonyl, which would be incompatible in the hydrometallation process with dibal-H. Our efforts accumulate to the first report of incorporation of all carbon quaternary centers that are substituted with unsaturated ester and aldehyde units in the EAS products; such a method facilitates the concise diastereo- and enantioselective synthesis of Pummerer's ketone and it's trans isomer. Further development of the above protocol towards the construction of tertiary stereogenic centers requires the design of new chiral sulfonate-containing imidazolinium salts as the ligand precursors and has lead to the employment of a broader range of alkenylboron species, which feature readily functionalizable motifs. Subsequent demonstrations in enantioselective synthesis of a variety of small molecule natural products showcase the utility. / Thesis (PhD) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Marc L. Snapper / Chapter 1. A Practical Synthesis of 3-Acyl Cyclobutanones by [2 + 2] Annulation. Mechanism and Utility of the Zn(II)-Catalyzed Condensation of alpha-Chloroenamines with Electron-Deficient Alkenes. We have developed a catalytic method for the synthesis of highly functionalized 3-acyl cyclobutanones which are useful building blocks for a variety of natural products. Methods for cyclobutanone synthesis have traditionally been limited to Lewis-acid promoted rearrangement of oxaspiropentanes or cyclizations of ketene and syntheses involving keteneiminium salts have required stoichiometric quantities of a Lewis acid. Furthermore, the mechanism for these types of cyclizations remains unknown. This portion of my research focused on an efficient, catalytic method for the synthesis of 3- acyl cyclobutanones and providing insight into the mechanism for cycloaddition. Chapter 2. Enantioselective Synthesis of Boron-Substituted Quaternary Carbons by NHC-Cu-Catalyzed Boronate Conjugate Additions to Unsaturated Carboxylic Esters, Ketones, or Thioesters. We have developed an enantioselective NHC-Cu-catalyzed conjugate addition of boronate esters to acyclic, trisubstituted alpha, beta-unsaturated carbonyl compounds. Enantioselective conjugate addition of a boronic acid pinacol ester through the use of bis(pinacolato)diboron [B2(pin)2,] to alpha, beta-unsaturated aliphatic and aryl esters promoted by 5 mol % of an NHC-Cu catalyst afforded tertiary beta-boryl carbonyls in high efficiency and enantioselectivity. Trisubstituted alpha, beta-unsaturated esters and thioesters were found to be reactive substrates in the presence of a stoichiometric quantity of methanol. Chapter 3. Metal-Free Catalytic C-Si Bond Formation in an Aqueous Medium and C-B Bond Formation in a Protic Medium. Enantioselective NHC-Catalyzed Silyl and Boryl Conjugate Additions to Cyclic and Acyclic alpha, beta-Unsaturated carbonyls. We have developed a method for enantioselective metal-free silyl conjugate additions through the use of dimethylphenylsilyl) boronic acid pinacol ester [PhMe2SiB(pin)] catalyzed by chiral N-heterocyclic carbenes (NHCs) in basic aqueous thf. Optimization of metal-free conditions demonstrated that the presence of water was required for high efficiency. alpha, beta-Unsaturated cyclic ketones and lactones were examined as substrates, and acyclic ketones, esters and aldehydes were also competent substrates for silyl conjugate addition. beta-Silyl carbonyls were isolated in up to >98% yield and >98:2 er. Chapter 4. Elucidation of Mechanism for Enantioselective NHC-Catalyzed Silyl Conjugate Addition. We propose a catalytic cycle for NHC-catalyzed enantioselective silyl conjugate addition. Mechanistic studies of NHC-catalyzed enantioselective silyl conjugate additions are presented. Optimization of conditions for an inefficient alpha, beta-unsaturated electron-deficient ketone provided insight into the roles for dbu and water. Kinetic data indicate that conjugate addition is first order in PhMe2SiB(pin) and carbene, and DFT calculations support the formation of an NHC-silyl anion as a reactive intermediate in the catalytic cycle. / Thesis (PhD) — Boston College, 2012. / Discipline: Chemistry.

Thesis advisor: Amir H. Hoveyda / Chapter 1 Catalytic Enantioselective Addition of Organoaluminum Reagents Catalytic methods involving the enantioselective addition of both commercially available as well as in situ generated organoaluminum reagents are reviewed. An overview of additions to aldehydes, ketones, and imines is provided as well as the difficulties and limitations of such transformations. Furthermore, additions to unsaturation adjacent to a leaving group to form a new stereogenic center are examined. Finally, conjugate addition reactions wherein an organoaluminum reagent is added to an olefin adjacent to a carbonyl or nitro group are discussed. Chapter 2 Synthesis of Quaternary Carbon Stereogenic Centers through Enantioselective Cu-Catalyzed Allylic Substitution with Alkenylaluminum Reagents A method for the formation of 1,4-diene containing quaternary stereogenic centers through catalytic enantioselective allylic substitution is disclosed. The addition of alkyl- and aryl-substituted alkenylaluminum reagents to trisubstituted allylic phosphates is promoted by 0.5–2.5 mol % of a sulfonate-containing bidentate N-heterocyclic carbene–copper complex. Products containing a quaternary stereogenic center as well as a newly formed terminal olefin are obtained in up to 97% yield and 99:1 er with high site selectivity (>98:2 SN2’:SN2). The requisite nucleophiles are generated in situ through hydroalumination of terminal alkynes. The utility of the method is demonstrated through a concise synthesis of natural product bakuchiol. Chapter 3 A Multicomponent Ni-, Zr-, Cu-Catalyzed Strategy for Enantioselective Synthesis of Alkenyl-Substituted Quaternary Carbons Despite the widespread use of conjugate addition in organic synthesis, few reports pertain to the addition of nucleophiles to acyclic systems and none in which the nucleophile is an alkene. Herein, we report the first examples of enantioselective conjugate addition of alkenylmetal reagents to trisubstituted enones to form all-carbon quaternary stereogenic centers. Alkenylaluminum nucleophiles are prepared through a site-selective Ni-catalyzed hydroalumination of terminal alkynes and the requisite E-trisubsituted enones are the products of a regioselective Zr-catalyzed carboalumination/acylation of a terminal alkyne. Products are obtained in up to 97% yield and 99:1 er. A model for enantioselectivity, supported by DFT calculations, is proposed. Chapter 4 Formation of Tertiary Centers through Catalytic Enantioselective Conjugate Addition of Alkenylaluminum Reagents to Acyclic Enones We have developed an enantioselective NHC–Cu catalyzed synthesis of tertiary centers in acyclic systems using in situ generated alkenylaluminum reagents, as current methods typically rely on Rh-catalysis at high temperatures with alkenyl boronic acids in protic solvents. Moreover, most examples include chalcone-derived substrates, which, while more reactive, often preclude further functionalization. With the current method, we are able to couple a variety of alkenyl nucleophiles with α,β-unsaturated ketones. E- or Z-silylalkenylaluminum reagents, derived from hydroalumination of silyl-protected alkynes, lead to products in good yields and high enantioselectivities. Additionally, both the α- and β-alkenylaluminum reagents participate in the reaction. Chapter 5 Development of N-Heterocyclic Carbene–Cu Catalyzed Allylic Substitution of Diboryl Methane to Morita-Baylis-Hillman Derived Allylic Phosphates We have developed a method for the coupling of a geminyl diboron reagent with Morita-Baylis-Hillman derived trisubstituted ester-containing allylic phosphates. With 10 mol % of an in situ generated NHC–Cu complex and 1.5 equivalents of the boron reagent, we are able to form the desired product in high regio- and enantioselectivity with a 2,5-ditert-butyl containing carbene. Simple aryl substituents as well as those containing a halogen or an electron-withdrawing group furnish the desired products in up to 85% yield and 98:2 er. Alkyl-containing substrates are also competent reaction partners, although longer chain aliphatics results in slightly diminished enantioselectivity. We are pursuing the application of this method to the synthesis of α-methylene lactones which can be further functionalized to natural products like tubulin polymerization inhibitor (–)-steganone and glaucoma medication (+)-pilocarpine. / Thesis (PhD) — Boston College, 2016. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Hak-fun Chow. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1981. / Bibliography: leaves 70-73.

This thesis describes the synthesis, characterisation and reactivity of new manganese and rhenium(I) NHC complexes, which have been investigated both thermally and photochemically and the results contrasted with existing phosphine analogues in the literature. Cp’Mn(CO)2(NHC) (NHC = IEt2Me2 1, IMes 2, IiPr2Me2 3 and IPr 4) were synthesised and investigated by TRIR spectroscopy. Loss of CO was observed after 355 nm irradiation to form agostically stabilised intermediates, which reformed the parent species by recombination with CO on the nanosecond timescale. Loss of NHC was not observed, in contrast to Cp’Mn(CO)2(PPh3) which lost both CO and PPh3 upon photolysis. [Re(NHC)(Bpy)(CO)3]BAr4F (NHC = IEt2Me2 5, IMes 6) were synthesised and investigated by TRIR spectroscopy and UV/Vis absorption and emission spectrometry. Inclusion of an NHC altered the excited state manifold of the complexes, favouring population of the 3MLCT over the 3IL excited state. The lowest energy excited state for both 5 and 6 proved to be a 3MLCT excited state at 298 and 77 K. In contrast, [Re(PPh3)(Bpy)(CO)3]BAr4F exhibited 3MLCT at 298 K, but 3IL at 77 K. A series of complexes, M(NHC)(CO)4X and M(NHC)2(CO)3X (M = Re, X = Cl; M = Mn, X = Br) formed upon reaction of the corresponding M(CO)5X species and free NHC. The substitution pattern was dictated by the steric bulk of the NHC. Generation of the corresponding cations by halide abstraction was investigated. M(NHC)2(CO)3X was found to form agostic stabilised species upon halide abstraction by NaBAr4F in CH2Cl2. Under the same conditions, Re(IPr)(CO)4Cl was found to form the dichloromethane complex, [Re(IPr)(CO)4(η1-CH2Cl2)]BAr4F. In C6H5F solution under an atmosphere of dihydrogen, the CH2Cl2 ligand could be displaced by H2 to form the dihydrogen species, [Re(IPr)(CO)4(H2)]BAr4F.

N-Heterocyclic carbenes (NHCs) are an important class of compounds responsible for a wide variety of chemical transformations. NHCs may be used as organocatalysts that permit non-traditional carbon carbon bond formations due to their renowned ability to invert the electrophilic character of aldehyde carbonyl groups, a concept otherwise known as polarity reversal or umpolung reactivity. Despite their ubiquity with respect to accessing the umpolung of aldehydes, fundamental studies of these reactive species are still rather limited and narrow in scope. As a result, clarifying and solving problems relevant to umpolung-themed asymmetric catalysis becomes quite challenging. In this regard, our work has been focused on a three-pronged approach towards providing a more unified understanding of these complex catalytic systems. First, we describe the synthesis of unprecedented carboxylate-tethered triazolium NHCs and use them in the intramolecular Stetter reaction to understand their function. Second, we describe the acidities of a broad range of both chiral and achiral NHCs that have never had their acidities assessed before and use them to construct the first linear free-energy relationships of their kind. Finally, we develop a simple and noninvasive experimental protocol in which we can quickly benchmark the performance of a series of chiral catalysts by way of single competition experiments. We anticipate that these studies will have direct implications on the development of novel NHC-catalyzed reactions.

2-Pyridinyl-2-pyrazinylmethanone (L4) is able to exist in the neat ketone form and gem-diol form (2-C5H4N)C(OH) 2(2-C4H3N2) (L4a) in its Ag(I) and Cu(II) complexes. Two isostructural Cu(II) complexes [Cu(L4 a)2X2·2H2O, X = C lO4-, BF4-] with the L4a ligand taking the chelating mode are formed, in which the different linkage modes of lattice water molecules between the Cu(L4 a)22+ units lead to different space groups in crystallization. Through versatile anion-pi(pyrazinyl ring) and hydrogen-bonding interactions, the Cu(L4a)22+ units are assembled into distinct 3-D metal-organic hybrid frameworks in these two complexes. Different ligation modes of L4 in its neat ketone and gem-diol forms are found in its silver(I) complexes that exhibit diverse network structures. / By tuning the counter anion, mu2-bridging 2,6-pyridinediylbis(4-pyridinyl)methanone (L2) via two terminal 4-pyridyl N atoms links Ag(I) ions into two distinct structural motifs in its silver(I) complexes, namely infinite helical chain and metallacyclophane, which are further assembled into higher-dimensional metal-organic frameworks through Ag···Ag, pi···pi, hydrogen-bonding, Ag···O=C, carbonyl···carbonyl, as well as unconventional anion-pi(pyridyl ring) interactions. Intermolecular dipolar carbonyl···carbonyl interaction of three principal types serves as a common dominant non-covalent interaction in the supramolecular conglomeration of these complexes. / Di-2-pyrazinylmethanone (L3) readily undergoes metal-assisted hydration reaction in its Ag(I), Cu(II), Co(II) and Cd(II) complexes, and is potentially useful for the construction of extended coordination networks with its gem-diol (2-C4H3N2)2C(OH) 2 (L3a) or anionic (2-C4H3N 2)2C(OH)CO- (L3b) form as an architectural moiety. A sheet-like net, an alpha-polonium topology of the NaCl-type and a rare 1-D nanotubular coordination architecture has been generated in its Ag(I) complexes through the tuning of counter-anions. Three isostructural complexes Cu(L3a)2X2· nH2O (n = 4.5; X = ClO 4-, BF4-, PF 6-) have been obtained and characterized. The 3-D host frameworks of these complexes are constructed from the linkage of mononuclear Cu(L3a)22+ metallotectons through a combination of hydrogen-bonding and anion-pi interactions, leading to honeycomb-like channels that accommodate guest water molecules. A cubane-like Co(II) cluster stabilized by L3b and the topological structure of Cd(II) complexes with L3a have also been obtained. / Di-2-pyridinylmethanone (di-2-pyridyl ketone) is a well-known versatile ligand among the basic building blocks for the construction of metal-organic hybrid materials. It can exist in its neat form, or in the hydrated gem-diol and alcoholated hemiketal forms. In this thesis, through modification of the heterocyclic ring and the bridging functional group, we have systematically synthesized a series of transition metal complexes of five carbonyl-bridged heterocycles (L1-L5) (see P. xi) and two structural analogs with sulfinyl and sulfonyl bridging groups (L6-L7), which are expected to provide flexible coordination bonding and additional non-covalent interactions in the generation of metal-organic hybrid frameworks. / In the two mononuclear Cu(II) complexes of 2,6-pyridinediylbis(3-pyridinyl)methanone (L1) with the ligand taking a chelating mode, four distinct types of unconventional intermolecular C=O···pi interactions between the carbonyl and pyridyl rings were identified. Moreover, the mu2-bridging L1 via two 3-pyridyl N atoms proves to be an excellent building block for the construction of disilver(I) metallacyclophanes with a [Ag2(L1) 2]2+ skeleton in a series silver(I) complexes. The [Ag 2(L1)2]2+ metallacycle functions as a secondary building unit to form infinite chains through Ag···O=C or argentophilic interactions, which are further assembled into a 3-D supramolecular structure via collective weak interactions including the anion-pi interaction. The employment of different Cd(II) and Hg(II) salts to react with the flexible L1 ligand has resulted in infinite chain, mononuclear, and 3-D network structures, in which L1 takes eta1-terminal, N,N-chelating, and mu2- and mu3-bridging modes. In these complexes, C--H···O, C--H···Cl--M hydrogen bonding, pi···pi, carbonyl···carbonyl, O(perchlorate)···C=O, as well as unconventional anion···pi(pyridyl ring) interactions, play important roles in consolidation of the supramolecular frameworks. / Sulfinyldipyrazine (L7) is capable of forming intriguing architectures in various sivler(I) salts, including a series of coordination polymers exhibiting (4,4) net, infinite chain and 3-D framework structures. A remarkable characteristic of L7 is that the electron-deficient pyrazinyl ring and the sulfonyl group provide potential bonding sites for lone-pair-aromatic interactions in the supramolecular assemblies, such as anion-pi and S=O···pi(pyrazinyl ring) interactions. The S=O moiety of the sulfonyl group exhibits an affinity for the pyrazinyl ring, which is evidenced by the existence of two types of such interaction in the silver(I) complexes of L7. (Abstract shortened by UMI.) / by Wan, Chongqing. / Adviser: Thomas C. W. Mak. / Source: Dissertation Abstracts International, Volume: 70-06, Section: B, page: 3504. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 172-190). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

He, Xiao. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references (leaves 75-83). / Abstracts in English and Chinese. / Acknowledgement --- p.I / Abstract --- p.II / 摘要 --- p.III / Abbreviation --- p.IV / List of Compounds --- p.VI / List of Figures --- p.VII / Contents --- p.IX / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Transition Metal-Carboranyl Complexes --- p.2 / Chapter 1.1.1 --- Late Transition Metal-Carboranyl Complexes --- p.2 / Chapter 1.1.2 --- Early Transition Metal-Carboranyl Complexes --- p.6 / Chapter 1.2 --- Transition Metal-Carboryne Complexes --- p.12 / Chapter 1.3 --- Five-Membered Heterocycles Incorporating Main Group Elements --- p.20 / Chapter 1.3.1 --- Synthesis and Reactivity of Boroles --- p.20 / Chapter 1.3.2 --- Synthesis and Reactivity of Phospholes --- p.24 / Chapter 1.3.3 --- Synthsis and Reactivity of Silole --- p.28 / Chapter 1.4 --- Our Objectives --- p.31 / Chapter Chapter 2 --- Nickelacycles Incorporating a Carboranyl Unit --- p.32 / Chapter 2.1 --- Introduction --- p.32 / Chapter 2.2 --- "Synthesis, Characterization and Reactivity of Nickelacycles Bearing (2-CPh2O-l,2-C2B10H10)2-Ligand" --- p.32 / Chapter 2.2.1 --- Synthesis and Characterization --- p.32 / Chapter 2.2.2 --- Reactivity Study --- p.34 / Chapter 2.2.3 --- X-ray Structure --- p.36 / Chapter 2.3 --- "Synthesis and Characterization of Nickelacycles Bearing [2-C(Ph)=N-l,2-C2B10H10]2- Ligand" --- p.44 / Chapter 2.3.1 --- Synthesis and Characterization --- p.44 / Chapter 2.3.2 --- X-ray Structure --- p.45 / Chapter Chapter 3 --- Five-membered Heterocycles of Main Group Elements Incorporating a Carboranyl Unit --- p.47 / Chapter 3.1 --- Synthesis and Characterization of Heterocycles Bearing Phosphorus Element --- p.47 / Chapter 3.2 --- Synthesis and Characterization of Heterocycles Bearing Silicon Element --- p.53 / Chapter 3.3 --- Synthesis and Characterization Heterocycles Bearing Boron Element --- p.58 / Chapter Chapter 4 --- Conclusion --- p.61 / Chapter Chapter 5 --- Experimental Section --- p.63 / References --- p.75 / Appendix --- p.84 / Chapter I. --- Crystal Data and Summary of Data Collection and Refinement --- p.84 / Chapter II. --- X-ray crystallographic data in CIF (electronic form)

The syntheses of a new class of polycyclic TriAmino DiCarbenes (TADCs), based on 3,9-diazajulolidine, and their precursors and adducts are described. Starting with 2,6-dimethyl-nitrobenzene, 2,6-bis ((alkylamino)methyl)anilines (alkyl = isopropyl, mesityl, and tert-butyl) were synthesized in 40% yield over five steps. These triamines were then di-cyclized stepwise to diformamidinium dications or formamidinium/2-methoxyformaminals using oxonium salts and trialkyl orthoformates. A diformamidinium dication was characterized by single-crystal X-ray diffractometry. Treatment with various bases, particularly lithium hexamethyldisilylazide, led to the novel TADCs and monocarbenes, two of which were isolated and characterized by 1H and 13C NMR spectroscopies. In both cases, treatment with elemental sulfur trapped the TADCs as dithiobiurets. No TADC-transition metal complexes were successfully isolated from reactions of the diformamidinium dications or LiHMDS TADC complex with a number of transition metal complexes. With the exception of these two cases, all other TADCs were not isolated because they rapidly reacted to form dimers, trimers, and tetramers. One of these dimers was isolated and its structure determined using 1D and 2D NMR spectroscopies, along with high-resolution electrospray ionization mass spectrometry. This revealed that the TADC had dimerized to form an ene-triamine, likely via 1,3-shift of a benzylic proton. Novel N-heterocyclic Carbene (NHC) complexes of molybdenum were also synthesized and characterized. Reaction of Cp2Mo2(CO)4 (Cp = C5H5) with dimesityl-imidazol-2-ylidenes (IMes) or dimesityl-imidazolidin-2-ylidenes (SIMes) yielded the molybdoradicals CpMo(CO)2(NHC) (NHC = IMes or SIMes). The carbonyl infrared stretching frequencies and the relative metal-to-NHC π-backbonding for IMes and SIMes complexes are compared. Reaction of the less bulky dimethyl-imidazol-2-ylidene (IMe) with Cp2Mo2(CO)4 yielded the Mo-Mo triple bond complex Cp2Mo2(CO)3(IMe) by CO substitution. This is the first example of an NHC-ligated metal-metal multiply bonded complex. Single crystal X-ray diffractometry of these new organomolybdenum and organodimolybdenum complexes is discussed.

Nature provides fascinating and complicated molecular structures which offer synthetic organic chemists amazing opportunities for the design of new strategies for natural product synthesis. Among these, nitrogen containing aza-heterocycles are of unparalleled importance in natural product, bioorganic, and medicinal chemistry. Pyridine and its derivatives in particular are the most common aza-heterocycles encountered in natural products, medicinal and materials chemistry. Pyridine derivatives also serve as precursors to functionalized piperidines, which are likewise common structural motifs in bioactive and functionalized materials. Thus, developing synthetic methods suitable for the manipulation of pyridine ring systems remains an important objective in synthetic organic chemistry. The functionalization of pyridine derivatives via manipulation at the benzylic position has been investigated. First, the nucleophilicity of the benzylic position of the 4-alkyl pyridine substrates was used to engage in Brønsted acid-catalyzed aldol-like cyclizations with attached carbonyl electrophiles. These conditions afforded substituted pyridines with functionalized lactams. These substrates underwent an unusual dehydration/oxidation reaction when treated with thionyl chloride. In a similar study, 1,2-dialkylimidazoles afforded nucleophilic 2-alkylidene imidazolines upon treatment with an electrophilic activating group such as Boc2O. Positioning a ketone electrophile with in an N1-alkyl side chain results in cyclization at the imidazole 2-position to afford fused ring imidazoles through an aldol-like cyclization reaction. The stereoselective synthesis of a tricyclic analogue of the bis(piperidine) alkaloid xestoproxamine C was also investigated. Dearomatization of a tricyclic pyridine derivative afforded an alkylidene dihydropyridine (anhydrobase) intermediate which was subjected to catalytic heterogeneous hydrogenation to install the correct relative stereochemistry about the bis(piperidine) ring system. Other key features of these model studies included development of an efficient ring-closing metathesis procedure to prepare macrocyclic derivatives of 3,4-disusbstituted pyridines, intramolecular cyclizations of alkylidene dihydropyridines to establish pyridine-substituted pyrrolidines and piperidines, successful homologation of pyridine-4-carboxaldehydes using formaldehyde dimethyl thioacetal monoxide (FAMSO), and application of B-alkyl Suzuki coupling to assemble substituted pyridines. Lastly, a study was done to assess the feasibility of synthesizing one of the two chiral precursors needed for the asymmetric synthesis of xestoproxamine C via enzyme catalyzed transesterification of symmetric 1,3-diols. This resulted in successful transesterification of a symmetric 1,3-diol substrate with high enantioselectivity.