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Chelate-driven ester oxidative addition to rhodium and formation of aryl amino acid ruthenium complexes.

机译：螯合物驱动的酯氧化成铑后形成芳基氨基酸钌络合物。

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Since known enzymatic and chemical methods for sequencing from the C-terminus fail to provide the generality and sensitivity of the Edman degradation, we propose an approach to C-terminal sequencing based on esterification of the carboxy terminus with an alcohol bearing ligating atoms which will have an affinity for low-valent transition metals. Achieving our goal of C-terminal sequencing requires chemospecific binding of a metal to the C-terminus of a protein, with a metal-protein ratio of 1:1. Subsequent oxidative addition of the ester C-O bond to the metal anchors the metal firmly at the C-terminus. The oxidative addition chemistry of alkyl and amino acid esters was studied. 2-((diphenylphosphino)methyl)quinolin-8-ol was synthesized from 2-methylquinolin-8-ol by protection, lithiation, phosphinylation, and deprotection. The corresponding acetate ester reacts with the rhodium (I) dimer, ;Long polypeptides are either enzymatically or chemically cleaved into small fragments to be sequenced by the Edman degradation. There is a need for reagents with more specificity which would permit cleavage of amide bonds in the vicinity of aromatic residues, phenylalanine, tyrosine, or tryptophan. Novel 5 ruthenium cyclopentadiene complexes of the general formula ;Upon addition of external ligands such as trimethylphosphine and N, N-dimethylhydrazine, the bound acetyl amide becomes uncoordinated. Chiral amino acids of N-acetyl-(L)-phenylalanine also react with the Rh(I) in a 1:1 ratio, yielding two products in a ratio of 4:1. The CbzGlyGly ester of 2-

机译：由于从C端进行测序的已知酶法和化学方法无法提供Edman降解的一般性和敏感性，因此我们提出了一种基于羧基端与带有连接原子的醇酯化的C端测序方法。对低价过渡金属的亲和力。要实现C末端测序的目标，需要金属与蛋白质的C末端进行化学特异性结合，金属与蛋白质的比例为1：1。随后将酯C-O键氧化加成到金属上，将金属牢固地锚定在C端。研究了烷基和氨基酸酯的氧化加成化学。由2-甲基喹啉-8-醇通过保护，锂化，次膦酰基化和脱保护来合成2-（（二苯基膦基）甲基）喹啉-8-醇。相应的乙酸酯与铑（I）二聚体反应；长多肽通过酶或化学方法裂解为小片段，并通过埃德曼降解法进行测序。需要具有更高特异性的试剂，该试剂将允许在芳族残基，苯丙氨酸，酪氨酸或色氨酸附近裂解酰胺键。通式为5的新型钌环戊二烯配合物;添加外部配体（如三甲基膦和N，N-二甲基肼）后，结合的乙酰基酰胺变得不配位。 N-乙酰基-（L）-苯丙氨酸的手性氨基酸也以1：1的比例与Rh（I）反应，从而以4：1的比例生成两种产物。 2-的CbzGlyGly酯

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Joubran, Camil.;
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Arizona State University.;

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授予单位 Arizona State University.;
学科 Chemistry Inorganic.;Chemistry Organic.
学位 Ph.D.
年度 1996
页码 210 p.
总页数 210
原文格式 PDF
正文语种 eng
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1. Rhodium-catalyzed asymmetric addition of arylboronic acids to γ-phthalimido-substituted-α,β-unsaturated carboxylic acid esters: an approach to y-amino acids [J] . Fuzhong Han, Jun Chen, Xiangyang Zhang Tetrahedron letters: The International Journal for the Rapid Publication of Preliminary Communications in Organic Chemistry . 2011,第7期

机译：铑催化的芳基硼酸不对称加成至γ-邻苯二甲酰亚胺基取代的α，β-不饱和羧酸酯：一种γ-氨基酸的方法
2. Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids to β-Phthaliminoacrylate Esters toward the Synthesis of β-Amino Acids [J] . Takahiro Nishimura, Jun Wang, Makoto Nagaosa, Journal of the American Chemical Society . 2010,第2期

机译：铑催化不对称加成芳基硼酸至β-邻苯二甲酸酯丙烯酸酯，以合成β-氨基酸
3. Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids to β-Phthaliminoacrylate Esters toward the Synthesis of β-Amino Acids [J] . Takahiro Nishimura*† Jun Wang‡ Makoto Nagaosa† Kazuhiro Okamoto† Ryo Shintani† Fuk-yee Kwong‡ Wing-yiu Yu‡ Albert S. C. Chan*‡ and Tamio Hayashi Journal of the American Chemical Society . 2010,第2期

机译：铑催化不对称加成芳基硼酸至β-邻苯二甲酸酯丙烯酸酯，以合成β-氨基酸
4. 1,4-Addition of Arylboronic Acids to p-Aryl-alpha,beta-unsaturated Ketones and Esters Catalyzed by a Rhodium(I)-chiraphos Complex [C] . Takashi Nishikata, Tetsuji Iyama, Hiroto Tachikawa Symposium on Organometallic Chemistry . 2006

机译：1,4-加入芳基硼酸至p-芳基-α，β-不饱和酮和由铑（I）催化的酯 - 富铬络合物
5. The Formation of 1,2-Dioxolanes: I. By the Acid-Catalyzed Addition of H2O2 to ss,gamma-Epoxy Ketones II. By the Chromium-Catalyzed Allylic Peroxidation of a Triterpene Using O2 III. By the Metal-Catalyzed Addition of O2 to Substituted ss-Keto Esters Via an alpha-Acyl Radical. [D] . Richert, Kathleen J. 2015

机译：1,2-二氧戊环的形成：I. H2O2酸催化加成至ss，γ-环氧酮II。通过使用O2 III对三萜进行铬催化的烯丙基过氧化。通过α-酰基自由基通过金属催化将O2取代为取代的ss-Keto酯。
6. Rhodium-catalyzed asymmetric 14-addition reactions of aryl boronic acids with nitroalkenes: reaction mechanism and development of homogeneous and heterogeneous catalysts [O] . Hiroyuki Miyamura, Kohei Nishino, Tomohiro Yasukawa, 2017

机译：铑催化的芳基硼酸与硝基烯烃的不对称14-加成反应：反应机理及均相和非均相催化剂的发展
7. 1,4-Addition of arylboronic acids to β-aryl-α,β-unsaturated ketones and esters catalyzed by a rhodium(I)-chiraphos complex for catalytic and enantioselective synthesis of selective endothelin A receptor antagonists [O] . Itoh, Takahiro, Mase, Toshiaki, Nishikata, Takashi, 2006

机译：1,4-芳基硼酸被铑（I）-Chiraphos络合物催化的β-芳基-α，β-不饱和酮和酯的催化和对映选择性合成选择性内皮素A受体拮抗剂

Chelate-driven ester oxidative addition to rhodium and formation of aryl amino acid ruthenium complexes.

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