Article
Multidisciplinary Sciences
Jinwei Sun, Yongze Zhou, Rui Gu, Xin Li, Ao Liu, Xuan Zhang
Summary: Here, the authors report a nickel-catalyzed method for the silylative alkylation of activated olefins using chlorosilanes and alkyl bromides. This approach enables the efficient synthesis of alkylsilanes with diverse structures and demonstrates good functional group tolerance. The method can also be applied for the functionalization of bioactive molecules.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Kai-Yi Zhang, Fang Long, Chuan-Chong Peng, Jin-Hui Liu, Li-Jun Wu
Summary: A Pd-catalyzed multicomponent cross-coupling reaction using K2S2O5 as a connector is reported for the first time to synthesize allylic sulfones from allyl esters and alkyl bromides. The reaction shows broad substrate generality, excellent functional group compatibility, and high regioselectivity (only E). Biologically active molecules including aspirin, menthol, borneol, and estrone are also highly compatible with this multicomponent cross-coupling reaction. Mechanistic studies suggest that the process of SO2 insertion into the C-Pd bond is involved in this transformation.
Article
Chemistry, Multidisciplinary
Xiaolong Yu, Hongling Zheng, Haonan Zhao, Boon Chong Lee, Ming Joo Koh
Summary: A novel iron-catalyzed three-component synthesis method has been developed for the regioselective union of bis(pinacolato)diboron, an alkenyl halide, and an olefin to produce homoallylic boronates. The reaction can generate products with tertiary or quaternary carbon centers in up to 87% yield as single regioisomers with complete retention of the olefin stereochemistry. Selective formation of trisubstituted E-alkenylboronates from cyclopropylidene-containing substrates was also observed, revealing unique reaction attributes distinct from previously reported pathways.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Jia-Jia Liao, Ren-Gui Tian, Shi-Kai Tian
Summary: An unprecedented reductive cross-coupling reaction has been developed through C-N bond cleavage, enabling the efficient synthesis of diverse alkene products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xing-Wei Gu, Xiao-Feng Wu
Summary: Transition metal-catalyzed carbonylation of alkyl halides is an efficient method for synthesizing aliphatic carbonyl-containing compounds. This paper discusses recent developments in the carbonylation reactions of alkyl bromides and chlorides catalyzed by abundant metals.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Kai Yang, Pengfei Wang, Ze-Ying Sun, Minjie Guo, Wentao Zhao, Xiangyang Tang, Guangwei Wang
Summary: In this study, a hydrogen-bonding controlled nickel-catalyzed regioselective cyclotrimerization of terminal alkynes was reported, yielding 1,3,5-trisubstituted benzenes with high regioselectivities. The method features a low-cost catalyst, mild reaction conditions, and excellent functional group compatibility. The Ni-B(OH)(2) complex generated in situ from NiCl2·DME and tetrahydroxydiboron may act as an active catalyst for this transformation.
Article
Chemistry, Organic
Mimi Xing, Huanhuan Cui, Chun Zhang
Summary: A novel nickel-catalyzed reductive cross-coupling method has been developed for constructing C-Si bonds under mild reaction conditions, allowing for the synthesis of structurally diverse organosilanes without Ni-catalyzed isomerization. The utility of this chemistry is demonstrated through further transformations of the product, while the radical mechanism of the reaction is elucidated through control experiments.
Article
Chemistry, Organic
Sen Yang, Hao Hu, Ming Chen
Summary: A highly efficient visible-light-induced elimination method for alkyl halides is presented, which selectively yields unactivated terminal olefins vital in organic synthesis.
Article
Chemistry, Organic
Sen Yang, Hao Hu, Ming Chen
Summary: A highly efficient method for visible-light-induced regio- and chemoselective elimination of alkyl halides yielding unactivated terminal olefins vital in organic synthesis is presented. The reaction, achieved through ligand control, exhibits remarkable regioselectivity and suppresses undesired side reactions, particularly 1,5-hydrogen atom transfer (HAT). This method favors primary alkyl halides while preserving secondary and tertiary alkyl bromides, thereby enabling the incorporation of terminal olefins in complex molecules for late-stage functionalization.
Article
Chemistry, Multidisciplinary
Yan-Dong Zhang, Xiao-Yu Li, Qian-Kun Mo, Wen-Bin Shi, Jia-Bao Zhao, Shou-Fei Zhu
Summary: In this study, we developed new Co complexes with cyclopropane-based diphosphine ligands that can catalyze highly chemo-, regio-, and stereoselective hydroboration reactions of unsymmetrical internal alkynes. These reactions exhibit unusual regioselectivity, leading to the synthesis of trisubstituted alkenylborates and alkenes with different stereochemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Hailong Wang, Haichao Huang, Chao Gong, Yong Diao, Jianmei Chen, Si-Hai Wu, Lianhui Wang
Summary: A chemo- and regioselective nickel-catalyzed reductive benzylarylation of unactivated alkenes with o-bromobenzyl chlorides is reported, utilizing electrophiles through a single-component double-site approach. The utility of this method is demonstrated through the concise synthesis of bioactive Indane compounds and postreaction functionalizations leading to structurally diverse scaffolds. Preliminary mechanistic investigations suggest a radical chain reaction mechanism.
Article
Chemistry, Organic
Peng Guo, Xiaobo Pang, Ke Wang, Pei-Feng Su, Qiu-Quan Pan, Guan-Yu Han, Qian Shen, Zhen-Zhen Zhao, Wenhua Zhang, Xing-Zhong Shu
Summary: In this study, we reported a nickel-catalyzed reductive Csp(3)-Ge coupling of alkyl bromides with chlorogermanes, providing a facile access to organogermanes. The reaction tolerates various functionalities and can be applied to the modification of bioactive molecules.
Article
Chemistry, Multidisciplinary
Minghao Zhang, Zhiyang Ye, Wanxiang Zhao
Summary: We developed a cobalt-catalyzed remote borylation reaction for the enantioselective functionalization of alkyl halides, which provides a robust approach for the synthesis of chiral organoboronates. This method is compatible with primary, secondary, and tertiary bromides, allowing access to a broad range of alkylboronates. Moreover, the borylation of aryl halides was also demonstrated using this catalytic system. Preliminary mechanistic studies suggest a radical reaction pathway for this remote borylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Geun Seok Lee, Daeun Kim, Soon Hyeok Hong
Summary: The use of alkyl chlorides in Pd-catalyzed Mizoroki-Heck coupling reactions remains a challenging issue due to the high thermodynamic barrier of alkyl chloride activation and the propensity of alkylpalladium complexes to undergo undesired beta-hydride elimination. However, this study demonstrates that alkyl chlorides, including tertiary ones, can efficiently participate in Mizoroki-Heck cross-coupling reactions under mild conditions via photoinduced Pd catalysis, offering great potential for late-stage functionalizations and molecular complexity.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Atul Kumar, Gulenur N. Khatun, Rodney A. Fernandes
Summary: An efficient, mild, and economical approach for the regioselective synthesis of 4-aryl/alkyl-1-peroxy-but-3-en-2-ols from 1-substituted-1,3-butadienes using hydroperoxides and catalyzed by TBAI has been achieved. This method is simple to operate, does not require dry conditions, and has excellent tolerance to a wide range of substrates, resulting in good yields of corresponding hydroxyperoxidates. Thus, an outstanding regioselective orthogonal dioxygenation in a diene system has been accomplished.
Article
Chemistry, Multidisciplinary
Gregory J. P. Perry, Hideki Yorimitsu
Summary: This Perspective discusses the use of sulfur(IV) compounds in transition-metal-free cross-coupling reactions and highlights the versatile reactivity of sulfur(IV) in designing new reagents, mediators, and catalysts.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Shuhei Akahori, Atsushi Kaga, Jinseok Kim, Hideki Yorimitsu, Dongho Kim, Hiroshi Shinokubo, Yoshihiro Miyake
Summary: In this study, C-4h-symmetric octaaza[8]circulenes were synthesized and exhibited enhanced antiaromaticity upon protonation. The protonation of the pyridine rings enhanced the contribution of the octaaza[8]circulenes' antiaromatic character.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Organic
Shunsuke Koyama, Fumiya Takahashi, Hayate Saito, Hideki Yorimitsu
Summary: Treatment of alkenyl carbamates with sodium dispersion and a co-existing boron electrophile leads to the formation of alkenylboronates through the reductive cleavage of the vinylic C-O bond, facilitated by the instant trapping of reactive organosodium species.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Shuo Wang, Igor Larrosa, Hideki Yorimitsu, Gregory J. P. Perry
Summary: The potassium salts of carboxylic acids are developed as efficient carboxylating agents through CO2 exchange. These carboxylates function as a combined source of CO2 and base/metalating agent, making them dual-function reagents. By using the salt of a commercially available carboxylic acid, this protocol provides a convenient and practical alternative to using CO2 gas or organometallic reagents, without the need for pressurized containers or strictly inert conditions. The reaction is mild, transition metal-free, and exhibits a wide range of substrate compatibility. The strategy showcased the ability to isotopically label biologically important molecules using low amounts of labeled CO2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yunosuke Takekawa, Masanari Nakagawa, Kazunori Nagao, Hirohisa Ohmiya
Summary: In this study, a quadruple catalysis system involving N-heterocyclic carbene, cobalt, photoredox, and Bronsted base is demonstrated to achieve branch-selective hydroacylation of styrenes with aromatic and aliphatic aldehydes. This protocol provides a convenient and atom-economical method for the synthesis of branched ketones from readily available materials by transferring a formyl hydrogen of aldehydes as a hydrogen radical equivalent onto the terminal carbon of an alkene through controlled electron and proton transfers.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Fumiya Takahashi, Hideki Yorimitsu
Summary: In this study, regio- and stereoselective synthesis of Tetraarylethylenes (TAEs) was achieved through sodium-promoted reductive anti-1,2-dimagnesiation of alkynes and palladium-catalyzed arylation. This method not only enables the synthesis of diarylacetylenes, but also allows for the synthesis of alkyl aryl acetylenes, expanding the range of possible TAEs.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Kazuhira Miwa, Shinobu Aoyagi, Toru Amaya, Takahiro Sasamori, Shogo Morisako, Takashi Kurogi, Hideki Yorimitsu
Summary: The curved and π-conjugated surface of bowl-shaped corannulene has been multiply methylated through in-situ iterative reduction/methylation sequences, resulting in exo-di-, -tetra-, and -hexamethylated corannulenes. Various analytical techniques have been used to reveal the molecular structures of the multimethylated corannulenes and the sequence of the multimethylation. This work has the potential to contribute to the controlled synthesis and characterization of multifunctionalized fullerenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Rikako Nakamura, Takeru Yamazaki, Yui Kondo, Miho Tsukada, Yusuke Miyamoto, Nozomi Arakawa, Yuto Sumida, Taketoshi Kiya, Satoshi Arai, Hirohisa Ohmiya
Summary: Researchers have developed a new method for caging/uncaging bioactive molecules using a photo-cleavable carbon-boron bond. This method allows for the caging of previously uncageable molecules, such as acetylcholine, providing a unique tool for optopharmacology to study neuronal mechanisms.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Tomohiko Sato, Somnath N. Karad, Jun Shimokawa, Hideki Yorimitsu
Summary: The regioselective anti-silyllithiation of propargylic amines provides an efficient route for the synthesis of alkenylsilanes. The reaction involves the formation of a stable alkenyllithium intermediate through intramolecular coordination of the nitrogen functional group. After treatment with an electrophile, the alkenyllithium intermediate is functionalized to yield tetrasubstituted allylic amines bearing a beta-silicon substituent.
Article
Chemistry, Physical
Hiroki Yamagishi, Jun Shimokawa, Hideki Yorimitsu
Summary: The multifaceted implementation of silanols in organic synthesis is reviewed in terms of advances in transition metal-catalyzed reactions. The major properties of silanols are summarized, including their use as nucleophiles to serve as bulky surrogates for water, as temporary ligands to control the regioselectivity of metal-catalyzed reactions, and as coupling partners for transferring functional groups. These summaries provide opportunities for future developments in silanol chemistry.
Article
Chemistry, Organic
Ziwei Zhang, Fumiya Takahashi, Takashi Kurogi, Hideki Yorimitsu
Summary: The preparation of vinylic lithium reagents from vinylic halides is common in organic synthesis, but not always easy. This study proposes a new method using silyl enolates of alkyl aryl ketones, which provides readily available and efficient vinylic lithium species. The reductive transformation of electron-rich silyl enolates has significant potential for various applications in organic synthesis, serving as an alternative to the Shapiro reaction.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Sara Suzuki, Soni Aman Govind, Kosuke Imamura, Hideki Yorimitsu, Hiroshi Shinokubo, Masahiro Higashi, Hirofumi Sato
Summary: The radical cyclization reaction in aqueous environment by Yorimitsu et al. was reexamined using the RISM-SCF-cSED method, a hybrid approach combining quantum chemistry and statistical mechanics for molecular liquids. The difference in barrier height between the forward reaction from the intermediate E-rot, the cyclization step, and the backward reaction is crucial for the reaction yield. By considering the effect of hydrogen bonding through the RISM theory, it was found that the barrier height for the forward reaction is lower, particularly in water. In other words, accounting for microscopic solvation effects clearly elucidates the disparity between water and DMSO solvents, explaining the significant acceleration of the reaction in the aqueous environment.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Multidisciplinary Sciences
Kenji Ota, Kazunori Nagao, Dai Hata, Haruki Sugiyama, Yasutomo Segawa, Ryosuke Tokunoh, Tomohiro Seki, Naoya Miyamoto, Yusuke Sasaki, Hirohisa Ohmiya
Summary: This study demonstrates a light-driven radical-polar crossover mechanism for the tertiary alkylation of phosphorus atoms in nucleotides, enabling the synthesis of alkylphosphonate structures that are difficult to obtain using existing methods.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Ryoto Oya, Kenji Ota, Masaaki Fuki, Yasuhiro Kobori, Masahiro Higashi, Kazunori Nagao, Hirohisa Ohmiya
Summary: The biomimetic design based on the iron(iv)-oxo porphyrin & pi;-cation radical species in cytochrome P450 enzymes has been extensively studied. In this study, the functions of this species were translated to an & alpha;-ketoacyl phosphonium species comprised of non-metal atoms and used as a light-activated oxygenation auxiliary for ortho-selective oxygenation of anilines. The process exhibited high regioselectivity and chemoselectivity.
Article
Chemistry, Multidisciplinary
Ryoto Oya, Kenji Ota, Masaaki Fuki, Yasuhiro Kobori, Masahiro Higashi, Kazunori Nagao, Hirohisa Ohmiya
Summary: The biomimetic design of a transition metal complex based on the iron(iv)-oxo porphyrin & pi;-cation radical species has been translated to an & alpha;-ketoacyl phosphonium species for ortho-selective oxygenation of anilines. Visible light irradiation activates the excited state of the auxiliary, which acts as a transient oxidant, providing high regioselectivity and chemoselectivity.
