- Synthesis and use of a cost-effective, aqueous soluble diazo transfer reagent – m-carboxybenzenesulfonyl azide
-
Herein, we report the preparation and use of m-carboxybenzenesulfonyl azide as a diazo transfer reagent. This compound is an inexpensive and potentially scalable alternative to many of the diazo transfer reagents currently available, most of which have hazards associated with their use. Its usefulness and suitability as a diazo transfer reagent was assessed on the basis of cost, safety and its effectiveness in diazo transfer to a variety of different substrates.
- O'Mahony, Rosella M.,Broderick, Caoimhe M.,Lynch, Denis,Collins, Stuart G.,Maguire, Anita R.
-
-
Read Online
- Regioselective Synthesis of Dihydrothiophenes and Thiophenes via the Rhodium-Catalyzed Transannulation of 1,2,3-Thiadiazoles with Alkenes
-
A method for the regioselective synthesis of a wide range of dihydrothiophenes was developed from the rhodium-catalyzed transannulation of 1,2,3-thiadiazoles with aliphatic, aromatic, and heteroaromatic alkenes. Tandem rhodium-catalyzed transannulation of 1,2,3-thiadiazoles with alkenes followed by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation was also demonstrated for the one-pot regioselective synthesis of various thiophenes. Advantages of the present method include a broad substrate scope, wide functional group compatibility, and high regioselectivity.
- Son, Jeong-Yu,Kim, Jonghye,Han, Sang Hoon,Kim, Sung Hong,Lee, Phil Ho
-
-
Read Online
- Sulfur-controlled and rhodium-catalyzed formal (3 + 3) transannulation of thioacyl carbenes with alk-2-enals and mechanistic insights
-
A rhodium-catalyzed denitrogenative formal (3 + 3) transannulation of 1,2,3-thiadiazoles with alk-2-enals is achieved, producing 2,3-dihydrothiopyran-4-ones in moderate to excellent yields. An inverse KIE of 0.49 is obtained, suggesting the reversibility of the oxidative addition of thioacyl Rh(i) carbenes to alk-2-enals. The late-stage structural modifications of steroid compounds are realized. Moreover, our studies show that thioacyl carbenes have different reactivities to those of α-oxo and α-imino carbenes, and highlight the importance of heteroatoms in deciding the reactivities of heterovinyl carbenes.
- Wu, Qiuyue,Dong, Ziyang,Xu, Jiaxi,Yang, Zhanhui
-
p. 3173 - 3180
(2021/04/21)
-
- A 'sulfonyl-azide-free' (SAFE) aqueous-phase diazo transfer reaction for parallel and diversity-oriented synthesis
-
Diazo transfer reactions are notoriously associated with the use of potentially explosive sulfonyl azides. The first 'sulfonyl-azide-free' (SAFE) protocol for producing diazo compounds from their active-methylene precursors via the Regitz diazo transfer reaction was developed and has displayed a remarkable substrate scope. It can be applied to generating arrays of diazo compounds for further evolution via combinatorial chemistry and a range of scaffold-generating transformations.
- Dar'In, Dmitry,Kantin, Grigory,Krasavin, Mikhail
-
supporting information
p. 5239 - 5242
(2019/05/08)
-
- Oxazolinyl-Assisted Ru(II)-Catalyzed C?H Functionalization Based on Carbene Migratory Insertion: A One-Pot Three-Component Cascade Cyclization
-
A rare, ruthenium-catalyzed, oxazolinlyl assisted C?H functionalization and three-component cascade cyclization for the synthesis of isoquinolinones via a metal-carbene migratory insertion is reported. The transformation is unique since it involves the fo
- Kumar, Gangam Srikanth,Khot, Nandkishor Prakash,Kapur, Manmohan
-
supporting information
p. 73 - 78
(2018/12/11)
-
- Rh(III)-catalyzed annulation of BOC-protected benzamides with diazo compounds: Approach to isocoumarins
-
A mild rhodium-catalyzed annulation of Boc-protected benzamides with diazo compounds via C?C/C?O bond formation has been explored. In the presence of [Cp*RhCl2]2, AgSbF6 and Cs2CO3, Boc-protected benzamides can be effectively annulated to yield isocoumarins in 0.5–2 h.
- Dong, Guangyu,Li, Chunpu,Liu, Hong
-
-
- Rhodium(III)-catalyzed [4+2] annulation via C-H activation: Synthesis of multi-substituted naphthalenone sulfoxonium ylides
-
A convenient Rh(III)-catalyzed C-H activation and cascade [4+2] annulation for the synthesis of naphthalenone sulfoxonium ylides has been developed. This method features perfect regioselectivity, mild and redox-neutral reaction conditions, and broad substrate tolerance with good to excellent yields. Preliminary mechanistic experiments were conducted and a plausible reaction mechanism was proposed. The new type naphthalenone sulfoxonium ylides could be further transformed into multi-substituted naphthols, which demonstrates the practical utility of this methodology.
- Song, Xiaohan,Han, Xu,Zhang, Rui,Liu, Hong,Wang, Jiang
-
-
- Rhodium(i)-catalyzed vinylation/[2 + 1] carbocyclization of 1,6-enynes with α-diazocarbonyl compounds
-
A sequential Rh(i)-catalyzed vinylation/[2 + 1]carbocyclization between enynes and diazo compounds has been developed. This transformation features a wide range of enynes and acceptor/acceptor diazo compounds, providing easy access to versatile vinyl-substituted azabicyclo[3.1.0]hexanes having a broad tolerance to functional groups.
- Huang, Junmin,Hu, Xinwei,Chen, Fengjuan,Gui, Jiao,Zeng, Wei
-
supporting information
p. 7042 - 7054
(2019/08/01)
-
- Atroposelective Phosphoric Acid Catalyzed Three-Component Cascade Reaction: Enantioselective Synthesis of Axially Chiral N-Arylindoles
-
An efficient organocatalytic atroposelective three-component cascade reaction of 2,3-diketoesters, aromatic amines, and 1,3-cyclohexanediones has been developed for the highly enantioselective synthesis of axially chiral N-arylindoles. The success of this method derives from the use of a newly developed second-generation chiral spirocyclic phosphoric acid as the catalyst. In addition, this protocol was extended to the synthesis of an axially chiral monophosphorus ligand.
- Wang, Lei,Zhong, Jialing,Lin, Xufeng
-
supporting information
p. 15824 - 15828
(2019/10/28)
-
- Rh(III)-Catalyzed C-H Activation of Benzoylacetonitriles and Tandem Cyclization with Diazo Compounds to Substituted Benzo [de] chromenes
-
Rh (III)-catalyzed C-H activation of benzoylacetonitriles in coupling with diazo compounds was developed to synthesize diversified substituted benzo[de]chromenes via a formal (4 + 2) cycloaddition with a diazo compound and subsequent tandem (4 + 2) cycloa
- Fang, Feifei,Zhang, Chunmei,Zhou, Chaofan,Li, Yazhou,Zhou, Yu,Liu, Hong
-
supporting information
p. 1720 - 1724
(2018/04/14)
-
- Rhodium(I)-Catalyzed Coupling-Cyclization of C=O Bonds with α-Diazoketones
-
An unprecedented intermolecular nucleophilic attack of C=X bonds (X = O and S) on the rhodium(I)-carbenes has been developed. This transformation allows for the coupling-cyclization of aroylamides with α-diazoketones and provides concise access to 2,4,5-trisubstituted 1,3-oxazoles and 1,3-thiazoles with a broad tolerance of functional groups.
- Chen, Ziyang,Hu, Xinwei,Huang, Junmin,Zeng, Wei
-
supporting information
p. 3980 - 3983
(2018/07/15)
-
- Iron-Catalyzed Annulation of 1,2-Diamines and Diazodicarbonyls for Diverse and Polyfunctionalized Quinoxalines, Pyrazines, and Benzoquinoxalines in Water
-
A novel and facile iron-catalyzed tandem annulation of o-phenylenediamines and diazocarbonyls in water for the construction of polyfunctionalized quinoxalines has been developed. The key strategy includes the one-pot domino N?H insertion, cyclization, and
- Pandit, Rameshwar Prasad,Kim, Sung Hong,Lee, Yong Rok
-
supporting information
p. 3586 - 3599
(2016/11/25)
-
- C-H Activation-Based Traceless Synthesis via Electrophilic Removal of a Directing Group. Rhodium(III)-Catalyzed Entry into Indoles from N-Nitroso and α-Diazo-β-keto Compounds
-
A distinct C-H activation-based traceless synthetic protocol via electrophilic removal of a directing group is reported, complementing the currently exclusively used nucleophilic strategy. Rh(III)-catalyzed, N-nitroso-directed C-H activation allows the development of a traceless, atom- and step-economic, cascade approach for the synthesis of indole skeletons, starting from readily available N-nitroso and α-diazo-β-keto compounds. Importantly, the cyclization/denitrosation reaction represents a hitherto unobserved reactivity pattern for the N-nitroso group.
- Wang, Jie,Wang, Mingyang,Chen, Kehao,Zha, Shanke,Song, Chao,Zhu, Jin
-
supporting information
p. 1178 - 1181
(2016/03/15)
-
- Asymmetric synthesis of 1H-pyrrol-3(2H)-ones from 2,3-diketoesters by combination of aldol condensation with benzilic acid rearrangement
-
An efficient two-step protocol for the asymmetric synthesis of 1H-pyrrol-3(2H)-one derivatives in 99% ee from conveniently accessed 2,3-diketoesters has been developed.
- Sha, Qiang,Arman, Hadi,Doyle, Michael P.
-
supporting information
p. 108 - 111
(2015/12/26)
-
- Controllable Rh(III)-Catalyzed Annulation between Salicylaldehydes and Diazo Compounds: Divergent Synthesis of Chromones and Benzofurans
-
A Rh(III)-catalyzed annulation between salicylaldehydes and diazo compounds with controllable chemoselectivity is described. AgNTf2 favored benzofurans via a tandem C-H activation/decarbonylation/annulation process, while AcOH led to chromones through a C-H activation/annulation pathway. The reaction exhibited good functional group tolerance and scalability. Moreover, only a single regioisomer of benzofuran was obtained due to the in situ decarbonylation orientation effect.
- Sun, Peng,Gao, Shang,Yang, Chi,Guo, Songjin,Lin, Aijun,Yao, Hequan
-
supporting information
p. 6464 - 6467
(2016/12/23)
-
- Synthesis of α-diazo-β-keto esters, phosphonates and sulfones via acylbenzotriazole-mediated acylation of a diazomethyl anion
-
We report a method for the synthesis of α-diazo-β-keto esters, phosphonates and sulfones via acylation of corresponding diazomethyl anions with N-acylbenzotriazoles. The N-o-amino-acylbenzotriazoles exhibited an unprecedented transphosphorylation reaction
- Pramanik, Mukund M. D.,Rastogi, Namrata
-
supporting information
p. 11567 - 11571
(2015/12/04)
-
- A simple one-pot preparation of diazoacetoacetate derivatives from aldehydes
-
(Chemical Equation Presented) Diazoacetoacetate derivatives can be simply and efficiently prepared from aldehydes in a one-pot process involving initial DBU-promoted "aldol" condensation with ethyl diazoacetate followed by in situ oxidation with IBX. Aryl, alkyl, and unsaturated aldehydes are all viable substrates.
- Erhunmwunse, Marvis O.,Steel, Patrick G.
-
experimental part
p. 8675 - 8677
(2009/04/11)
-