Unraveling origin of chemoselectivity and regioselectivity of iridium‐catalyzed B(4)–H functionalization of o‐carborane by alkyne DOI
Zitong Chen, Jiying Liu, Jiabin Liu

et al.

Journal of Physical Organic Chemistry, Journal Year: 2022, Volume and Issue: 36(2)

Published: Sept. 7, 2022

Abstract Functionalization at target site is an extremely challenging subject for surface modification of o ‐carborane. It a common tactic to introduce directing group onto the C(2)–H vertex induce exclusive B(4,5)–H functionalizations. In this study, was investigated. The computational results indicate that formal [4 + 2] annulation going via reductive elimination mechanism has kinetic priority than alkenylation decarboxylation mechanism. This in excellent agreement with experimental carborano‐isocoumarin as major product. Given alkyne insertion product, protonation alkene likely occur before followed by carborane. HOPiv regioselectivity determining step, and non‐covalent interaction analysis discloses it steric repulsion methyl on C(1) atom carborane towards iridacycle Cp * causes higher barrier B(3)–H activation, which finally leads specific B(4)–H functionalization.

Language: Английский

HTE and machine learning-assisted development of iridium(i)-catalyzed selective O–H bond insertion reactions toward carboxymethyl ketones DOI

Yougen Xu,

Feixiao Ren,

Lebin Su

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1153 - 1159

Published: Jan. 1, 2023

By combining HTE and machine learning technologies, an iridium( i )-catalyzed highly selective O–H bond insertion reaction of carboxylic acids sulfoxonium ylides was developed, extensive space exploration accomplished.

Language: Английский

Citations

18
Photocatalytic synthesis of dual acylmethylation derivates of indole[2,1-a]isoquinolinones via tandem cyclization/C3 acyl methylation DOI
Zongbo Xie, Wenli Li, Weiwei Zhang

et al.

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 580, P. 115058 - 115058

Published: April 15, 2025

Language: Английский

Citations

1
Iridium(III)-Catalyzed B(4)-Acylmethylation and B(3,5)-Diacylmethylation from o-Carboranes and Sulfoxonium Ylides DOI
Gi Hoon Ko, Kyusik Um, Hee Chan Noh

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(8), P. 1604 - 1609

Published: Feb. 17, 2022

An iridium(III)-catalyzed regioselective acylmethylation of the cage B(4)-H bond in o-carborane acids with sulfoxonium ylides is demonstrated through activation ethanol under very mild conditions, affording a number B(4)-acylmethylated o-carboranes. Additionally, selective sequential B(4)- and B(6)-acylmethylation reactions finally gave B(3,5)-diacylmethylated o-carboranes one pot.

Language: Английский

Citations

24
One-pot synthesis of 3-trifluoromethylbenzo[b][1,4]oxazines from CF3-imidoyl sulfoxonium ylides with 2-bromophenols DOI

Mingshi Pan,

Yixin Tong,

Xiaodong Qiu

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(89), P. 12443 - 12446

Published: Jan. 1, 2022

Herein, a method to access 3-trifluoromethyl-1,4-benzoxazines from CF3-imidoyl sulfoxonium ylides and 2-bromophenols has been demonstrated. This synthetic protocol proceeds via one-pot two-step sequence that includes the lithium-bromide-promoted O-H insertion of annulation, merits broad substrate scope, excellent functional tolerance operational simplicity, which provides an alternative means obtaining CF3-substituted heterocycles.

Language: Английский

Citations

21
Iridium-Catalyzed Diastereo- and Enantioselective [4 + 1] Cycloaddition of Hydroxyallyl Anilines with Sulfoxonium Ylides DOI

Chunlan He,

Yaping Tang,

Shengbiao Tang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(25), P. 4621 - 4626

Published: June 15, 2023

We present here an iridium-catalyzed diastereo- and enantioselective [4 + 1] cycloaddition reaction of hydroxyallyl anilines with sulfoxonium ylides under mild conditions, leading to 3-vinyl indolines in moderate good yields excellent enantioselectivities. Control experiments disclosed a plausible mechanism.

Language: Английский

Citations

13
Recent Advance in Transition Metal‐Catalyzed Carboxylic Acid Guided B−H Functionalization of Carboranes DOI
Qian Wang, Bifu Liu,

Kejun Feng

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(24), P. 4174 - 4188

Published: Dec. 1, 2022

Abstract Carboranes, a three‐dimensional class of carbon‐boron molecular clusters with remarkable electronic, physical, chemical characteristics, have proved as useful building blocks in boron neutron capture therapy agents, supramolecular design, optoelectronics, nanomaterials and organometallic/coordination chemistry. Thus, various organic modifications the B−H C−H functionalities carboranes been developed. These methods great success utilize directing groups, such carboxylic acids, to achieve selective functionalization carboranes. The carboxyl group can be easily introduced then removed after reactions. On other hand, assisted by highly regioselective electrophilic attack at electron‐rich positions B(4) B(5) cage generates five‐membered metallacyclic intermediates, which undergo further transformation. In this review, we show that transition metal‐catalyzed decarboxylation cross coupling reactions offer an opportunity for direct activation magnified image

Language: Английский

Citations

18
Directing Group Assisted Transition Metal Catalyzed Selective BH Functionalization of o-Carboranes DOI
Zuowei Xie, Jie Zhang

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: June 11, 2024

Abstract Carboranes are a type of molecular clusters consisting carbon, hydrogen, and boron atoms. They possess unique characteristics, such as three-dimensional aromaticity, icosahedral geometry, robustness. Functionalized carboranes have been utilized in various fields, including medicine, materials, organometallic/coordination chemistry. In this context, selective functionalization o-carboranes has received tremendous attention, specifically the regio- enantioselective modification ten chemically similar BH vertices within carborane cage. recent years, significant progress made catalytic vertex-specific functionalization, well achieving cage BH. This review provides an overview advancements research field. 1 Introduction 2 Carboxy-Assisted Functionalization 2.1 Formation B–C Bonds 2.2 B–N 2.3 B–O 2.4 B–X 2.5 Consecutive B–Y (Y = N, O) 3 N-Based Directing-Group-Assisted B–H 3.1 Acylamino Directing Group 3.2 Amide 3.3 Pyridyl 3.4 Imine 4 Phosphinyl-Assisted Cage 5 Bidentate-Directing-Group-Assisted 6 Other 7 Conclusions

Language: Английский

Citations

3
Post-coordination of Ru(II) Controlled Regioselective B(4)–H Acylmethylation of o-Carboranes with Sulfoxonium Ylides DOI Creative Commons
Hou‐Ji Cao, Jiaxin Li,

Jia-Hui Yan

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Despite significant progress in the B-H functionalization of carboranes, development cost-effective catalytic systems devoid noble metals, coupled with mechanistic validation regioselectivity control, remains a formidable challenge. Herein, we disclose an Ag salt-free, redox-neutral, and inexpensive ruthenium(ii)-catalyzed protocol that enables exclusive B(4)-H acylmethylation o-carboranes through novel post-coordination strategy. By exploiting weakly coordinating carboxylic acid as traceless directing group, this method achieves excellent mono-site selectivity for B-C(sp3) bond formation using diverse sulfoxonium ylides, demonstrating both functional group tolerance synthetic scalability. This work not only establishes practical platform but also addresses critical questions unresolved prior analogous studies. Through deuterium labeling, situ high-resolution mass spectrometry (HRMS) tracking, single-crystal X-ray analysis Ru intermediates, unequivocally demonstrate originates from unique mode Ru(ii). The catalyst simultaneously engages enolizable acylmethyl moiety mono-acylated intermediate, thereby dictating activation trajectory. Our findings establish generalizable regiocontrolled carborane while defining paradigms transition metal-mediated chemistry.

Language: Английский

Citations

0
Iridium-Catalyzed Selective B(4)–H Amination of o-Carboranes with Anthranils DOI
Lin‐Bao Zhang, Zuowei Xie

Organic Letters, Journal Year: 2022, Volume and Issue: 24(39), P. 7077 - 7081

Published: Sept. 23, 2022

We report here a catalytic selective cage B4-H amination of o-carboranes employing an Ir(III) complex as catalyst and anthranils aminating agents, leading to large class B4-aminated with very high yields broad substrate scope under mild conditions without any oxidants. In these reactions, the carboxyl group serves traceless directing unit determine site selectivity degree substitution.

Language: Английский

Citations

13
Unexpected Copper-Catalyzed Cascade Reaction of 1,6-Enynes with Sulfoxonium Ylides DOI
Hong Zhang,

Jieyin He,

Wendi Xu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(39), P. 7095 - 7100

Published: Sept. 26, 2022

An unprecedented copper-catalyzed cascade reaction of 1,6-enynes with sulfoxonium ylides is reported, providing a series structurally intriguing 2,3-disubstituted indolines bearing conjugated dienone functionality at the 3-position in moderate to excellent yields good chemo-, regio-, and diastereoselectivities under mild conditions. Importantly, sulfoxonium-ylide-derived copper-carbene herein exhibits quite different reactivity from that diazo copper-carbene. A rational mechanism, an initial ammonium ylide rather than allene formation, proposed.

Language: Английский

Citations

13