{"id":129,"date":"2018-12-15T23:10:32","date_gmt":"2018-12-15T23:10:32","guid":{"rendered":"https:\/\/people.smu.edu\/46760177\/?page_id=129"},"modified":"2018-12-15T23:10:32","modified_gmt":"2018-12-15T23:10:32","slug":"research-2","status":"publish","type":"page","link":"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/research-2\/","title":{"rendered":"Research"},"content":{"rendered":"<div class=\"et_d4_element et_pb_section et_pb_section_0  et_pb_css_mix_blend_mode et_section_regular et_block_section\" >\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_d4_element et_pb_row et_pb_row_0  et_pb_css_mix_blend_mode et_block_row\">\n\t\t\t\t<div class=\"et_d4_element et_pb_column_4_4 et_pb_column et_pb_column_0  et_pb_css_mix_blend_mode et-last-child et_block_column\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_module et_d4_element et_pb_text et_pb_text_0  et_pb_text_align_left et_pb_bg_layout_light\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_text_inner\"><h1 style=\"text-align: center\"><span style=\"font-size: x-large;font-family: 'Coda Caption'\"><strong>RESEARCH APPROACH<\/strong><\/span><\/h1>\n<p id=\"h.p_ID_34\" class=\"zfr3Q\"><\/div>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_divider et_pb_divider_0 et_pb_space\"><div class=\"et_pb_divider_internal\"><\/div><\/div><div class=\"et_pb_module et_d4_element et_pb_text et_pb_text_1  et_pb_text_align_left et_pb_bg_layout_light\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_text_inner\"><p><span style=\"font-family: Arial;font-weight: normal;font-size: large\"><strong>Cu-directed hydroxylation of C-H bonds<\/strong><\/span><\/p><\/div>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_text et_pb_text_2  et_pb_text_align_left et_pb_bg_layout_light\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_text_inner\"><p>In organic synthesis, an elegant way to overcome the selectivity issues associated with the formation of radicals is the use of directing groups (DG). In collaboration with Prof. Phil Baran, we studied the mechanism by which Cu promotes the intramolecular g-hydroxylation of sp<sup>3<\/sup> C-H bonds, which allowed a redesign of the oxidation conditions to use cheaper reagents and milder conditions with improved overall yields (<em>J. Org. Chem.<\/em> <strong>2017<\/strong>, <em>82<\/em>, 7887). Our lab later discovered that other sp<sup>2<\/sup> and sp<sup>3<\/sup> C-H substrates could also be oxidized using imino-pyridine DGs, Cu and H<sub>2<\/sub>O<sub>2<\/sub> (<em>Inorg. Chem.<\/em> <strong>2019<\/strong>, <em>58<\/em>, 7584). In both cases, we proposed the formation of a mononuclear Cu<sup>II<\/sup>OOH core prior to C-H hydroxylation, suggesting that mononuclear Cu\/O<sub>2<\/sub> species could be formed in Cu-dependent mononooxygenases. New research directions include the utilization of DGs with varying denticity and using this approach to develop synthetically useful transformations (e.g. enantioselective hydroxylations).<\/p><\/div>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_image et_pb_image_0\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<span class=\"et_pb_image_wrap \"><img loading=\"lazy\" decoding=\"async\" width=\"646\" height=\"286\" src=\"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2020\/10\/Picture1.png\" alt=\"\" title=\"Picture1\" srcset=\"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2020\/10\/Picture1.png 646w, https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2020\/10\/Picture1-300x133.png 300w\" sizes=\"(max-width: 646px) 100vw, 646px\" class=\"wp-image-1785\" \/><\/span>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_divider et_pb_divider_1 et_pb_space\"><div class=\"et_pb_divider_internal\"><\/div><\/div><div class=\"et_pb_module et_d4_element et_pb_text et_pb_text_3  et_pb_text_align_left et_pb_bg_layout_light\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_text_inner\"><p><span style=\"font-family: Arial;font-weight: normal;font-size: large\"><strong>Structure, spectroscopy and reactivity of 3d metal complexes bearing bidentate redox-active ligands with tunable H-bonding donors<\/strong><\/span><\/p><\/div>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_text et_pb_text_4  et_pb_text_align_left et_pb_bg_layout_light\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_text_inner\"><p>An alternative approach to avoid the formation of radical species in 3d metal-catalyzed organic synthesis is the use of redox-active ligands. In 2018, we reported that Cu complexes bearing bidentate redox-active ligands with tunable H-bonding groups catalyzed the aerobic oxidation of alcohols under mild conditions (<em>J. Am. Chem. Soc<\/em>., <strong>2018<\/strong>, <em>140<\/em>, 16625). We found that these unique ligands donated e<sup>\u2212<\/sup> and stabilized Cu\/O<sub>2<\/sub> species via H-bonding, and that the mechanism of alcohol oxidation was unprecedented for galactose-oxidase model systems. New research directions include the systematic study of these H-bonding interactions, the development of catalysts for biologically relevant reactions and the characterization and reactivity of \u201chigh-valent\u201d metal complexes.<\/p>\n<p id=\"h.p_ID_65\" class=\"zfr3Q\" style=\"text-align: justify\"><\/div>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_image et_pb_image_1 et_animated et-waypoint\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<span class=\"et_pb_image_wrap \"><img loading=\"lazy\" decoding=\"async\" width=\"396\" height=\"274\" src=\"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2020\/10\/Picture2.png\" alt=\"\" title=\"Picture2\" srcset=\"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2020\/10\/Picture2.png 396w, https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2020\/10\/Picture2-300x208.png 300w\" sizes=\"(max-width: 396px) 100vw, 396px\" class=\"wp-image-1786\" \/><\/span>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_divider et_pb_divider_2 et_pb_space\"><div class=\"et_pb_divider_internal\"><\/div><\/div><div class=\"et_pb_module et_d4_element et_pb_text et_pb_text_5  et_pb_text_align_left et_pb_bg_layout_light\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_text_inner\"><p><span style=\"font-family: Arial;font-weight: normal;font-size: large\"><strong>Monooxygenase-like reactivity of 3d metal complexes bearing tridentate redox-active ligands with tunable H-bonding donors<\/strong><\/span><\/p><\/div>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_text et_pb_text_6  et_pb_text_align_left et_pb_bg_layout_light\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_text_inner\"><p>Inspired by the active site of LPMO, we have recently reported the synthesis of a CuOH complex bearing an analogous tridentate ligand. This CuOH core was oxidized to three molecular oxidation states and that these \u201chigh-valent\u201d species perform two consecutive <span>H<\/span>\u009f abstractions from phenolic substrates via <span>H<\/span>\u009f transfer (<em>J. Am. Chem. Soc., <\/em><strong>2020<\/strong><span>, <em>142<\/em>, 12265<\/span><em>). <\/em><span>We will utilize these ligands to study intramolecular H-bonding interactions (between the anion and the H-bond donor), to develop metal complexes capable of functionalizing C-H bonds (hydroxylations, C-N bond formation, etc.), and to synthesize and characterize Cu-oxyl species (the \u201clost\u201d oxidant).\u00a0\u00a0\u00a0 <\/span><\/p><\/div>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_image et_pb_image_2 et_animated et-waypoint\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<span class=\"et_pb_image_wrap \"><img loading=\"lazy\" decoding=\"async\" width=\"614\" height=\"252\" src=\"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2020\/10\/Picture3.png\" alt=\"\" title=\"Picture3\" srcset=\"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2020\/10\/Picture3.png 614w, https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2020\/10\/Picture3-300x123.png 300w\" sizes=\"(max-width: 614px) 100vw, 614px\" class=\"wp-image-1787\" \/><\/span>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_divider et_pb_divider_3 et_pb_space\"><div class=\"et_pb_divider_internal\"><\/div><\/div><div class=\"et_pb_module et_d4_element et_pb_text et_pb_text_7  et_pb_text_align_left et_pb_bg_layout_light\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_text_inner\"><p><span style=\"font-family: Arial;font-weight: normal;font-size: large\"><strong>New Bio-Inspired Catalysts for Practical Organic Synthesis<\/strong><\/span><\/p><\/div>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_text et_pb_text_8  et_pb_text_align_left et_pb_bg_layout_light\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<div class=\"et_pb_text_inner\"><p>Enzymatic catalytic transformations have inspired synthetic chemists to design simplified catalytic systems that could emulate and\/or overcome these natural processes. Many researchers have expended efforts to explore new routes in the conversion of inert C-H bonds to value-added products. This part of the scientific project will focus on the development of catalysts based on the methodical design of first row metal complexes for the catalytic transformation of C-H and C=C bonds to selective C-O bond formation (hydroxylations, cis-dihydroxylatyion and epoxidation), C-N formation (aminations, aziridinations), C-C formation (cyclopropanation), and C-X halogenations (X = F, Cl, Br, I). Our efforts will concentrate on building a library of synthetic tools for cheap, environmentally sustainable, chemo- and stereoselective chemical transformations of complex molecules.<\/p>\n<p>&nbsp;<\/p><\/div>\n\t\t\t<\/div><div class=\"et_pb_module et_d4_element et_pb_image et_pb_image_3 et_animated et-waypoint\">\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t<span class=\"et_pb_image_wrap \"><img loading=\"lazy\" decoding=\"async\" width=\"472\" height=\"202\" src=\"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2018\/12\/unnamed-3-153ezqq.png\" alt=\"\" title=\"\" srcset=\"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2018\/12\/unnamed-3-153ezqq.png 472w, https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-content\/uploads\/sites\/9\/2018\/12\/unnamed-3-153ezqq-300x128.png 300w\" sizes=\"(max-width: 472px) 100vw, 472px\" class=\"wp-image-677\" \/><\/span>\n\t\t\t<\/div>\n\t\t\t<\/div>\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t\t\n\t\t\t<\/div>\n\t\t\t\t\n\t\t\t\t\n\t\t\t<\/div>\n","protected":false},"excerpt":{"rendered":"","protected":false},"author":8,"featured_media":0,"parent":0,"menu_order":0,"comment_status":"closed","ping_status":"closed","template":"","meta":{"_et_pb_use_builder":"on","_et_pb_old_content":"","_et_gb_content_width":"","footnotes":""},"class_list":["post-129","page","type-page","status-publish","hentry"],"_links":{"self":[{"href":"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-json\/wp\/v2\/pages\/129","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-json\/wp\/v2\/pages"}],"about":[{"href":"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-json\/wp\/v2\/types\/page"}],"author":[{"embeddable":true,"href":"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-json\/wp\/v2\/users\/8"}],"replies":[{"embeddable":true,"href":"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-json\/wp\/v2\/comments?post=129"}],"version-history":[{"count":0,"href":"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-json\/wp\/v2\/pages\/129\/revisions"}],"wp:attachment":[{"href":"https:\/\/groups.chem.cmu.edu\/garcia-bosch\/wp-json\/wp\/v2\/media?parent=129"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}