- METHODS OF BORYLATION AND USES THEREOF
-
The present invention relates, in general terms, to methods of borylation and uses thereof. In particular, the present invention provides a method of borylating an alkene compound by contacting the compound with a boron compound, a Fe pre-catalyst and a protic additive. The borylation occurs at a vicinal (β) position to an electron donating or electron withdrawing moiety of the compound.
- -
-
Page/Page column 61-62
(2021/04/30)
-
- Visible-Light Controlled Divergent Catalysis Using a Bench-Stable Cobalt(I) Hydride Complex
-
While the use of visible light in conjunction with transition metal catalysis offers powerful opportunities to switch between on/-off states of catalytic activity, the next frontier would be the ability to switch the actual function of the catalyst and resulting products. Here we report such an example of multi-dimensional catalysis. Featuring an easily prepared, bench-stable cobalt(I) hydride complex in conjunction with pinacolborane, we can switch the reaction outcome between two widely employed transformations, olefin migration and hydroboration, with visible light as the trigger.
- Beltran, Frédéric,Bergamaschi, Enrico,Teskey, Christopher J.
-
supporting information
p. 5180 - 5184
(2020/04/22)
-
- A Pd-Catalyzed Site-Controlled Isomerization of Terminal Olefins
-
An effective Pd-catalyzed isomerization of olefins with 2-PyPPh2 as the ligand is described. A wide variety of trans-2-olefins bearing various functional groups can be obtained with high regio- A nd stereoselectivity under mild reaction conditions. The ligand is crucial for the reaction.
- Ren, Wenlong,Sun, Fei,Chu, Jianxiao,Shi, Yian
-
supporting information
p. 1868 - 1873
(2020/03/03)
-
- Iron-Catalyzed Tunable and Site-Selective Olefin Transposition
-
The catalytic isomerization of C-C double bonds is an indispensable chemical transformation used to deliver higher-value analogues and has important utility in the chemical industry. Notwithstanding the advances reported in this field, there is compelling demand for a general catalytic solution that enables precise control of the C═C bond migration position, in both cyclic and acyclic systems, to furnish disubstituted and trisubstituted alkenes. Here, we show that catalytic amounts of an appropriate earth-abundant iron-based complex, a base and a boryl compound, promote efficient and controllable alkene transposition. Mechanistic investigations reveal that these processes likely involve in situ formation of an iron-hydride species which promotes olefin isomerization through sequential olefin insertion/β-hydride elimination. Through this strategy, regiodivergent access to different products from one substrate can be facilitated, isomeric olefin mixtures commonly found in petroleum-derived feedstock can be transformed to a single alkene product, and unsaturated moieties embedded within linear and heterocyclic biologically active entities can be obtained.
- Yu, Xiaolong,Zhao, Haonan,Li, Ping,Koh, Ming Joo
-
supporting information
p. 18223 - 18230
(2020/12/04)
-
- Cobalt(II)-Catalyzed Stereoselective Olefin Isomerization: Facile Access to Acyclic Trisubstituted Alkenes
-
Stereoselective synthesis of trisubstituted alkenes is a long-standing challenge in organic chemistry, due to the small energy differences between E and Z isomers of trisubstituted alkenes (compared with 1,2-disubstituted alkenes). Transition metal-catalyzed isomerization of 1,1-disubstituted alkenes can serve as an alternative approach to trisubstituted alkenes, but it remains underdeveloped owing to issues relating to reaction efficiency and stereoselectivity. Here we show that a novel cobalt catalyst can overcome these challenges to provide an efficient and stereoselective access to a broad range of trisubstituted alkenes. This protocol is compatible with both mono- and dienes and exhibits a good functional group tolerance and scalability. Moreover, it has proven to be a useful tool to construct organic luminophores and a deuterated trisubstituted alkene. A preliminary study of the mechanism suggests that a cobalt-hydride pathway is involved in the reaction. The high stereoselectivity of the reaction is attributed to both a π-πstacking effect and the steric hindrance between substrate and catalyst.
- Zhang, Sheng,Bedi, Deepika,Cheng, Lu,Unruh, Daniel K.,Li, Guigen,Findlater, Michael
-
supporting information
p. 8910 - 8917
(2020/12/23)
-
- ISOMERIZATION OF ALKENES
-
The present invention relates to an isomerization method for alkenes, comprising of reaction an alkene with a Ni(I)-compound. By this method, E-Alkenes are obtained in excellent yield.
- -
-
Page/Page column 20-21; 23-24
(2020/04/25)
-
- Nickel-Catalyzed Decarboxylative Alkenylation of Anhydrides with Vinyl Triflates or Halides
-
Decarboxylative cross-coupling of aliphatic acid anhydrides with vinyl triflates or halides was accomplished via nickel catalysis. This methodology works well with a broad array of substrates and features abundant functional group tolerance. Notably, our approach addresses the issue of safe and environmental installation of methyl or ethyl group into molecular scaffolds. The method possesses high chemoselectivity toward alkyl groups when aliphatic/aromatic mixed anhydrides are involved. Furthermore, diverse ketones could be modified with our strategy.
- Chen, Hui,Sun, Shuhao,Liao, Xuebin
-
supporting information
p. 3625 - 3630
(2019/05/24)
-
- E-Olefins through intramolecular radical relocation
-
Full control over the selectivity of carbon-carbon double-bond migrations would enable access to stereochemically defined olefins that are central to the pharmaceutical, food, fragrance, materials, and petrochemical arenas. The vast majority of double-bond migrations investigated over the past 60 years capitalize on precious-metal hydrides that are frequently associated with reversible equilibria, hydrogen scrambling, incomplete E/Z stereoselection, and/or high cost. Here, we report a fundamentally different, radical-based approach.We showcase a nonprecious, reductant-free, and atom-economical nickel (Ni)(I)-catalyzed intramolecular 1,3-hydrogen atom relocation to yield E-olefins within 3 hours at room temperature. Remote installations of E-olefins over extended distances are also demonstrated.
- Kapat, Ajoy,Sperger, Theresa,Guven, Sinem,Schoenebeck, Franziska
-
p. 391 - 396
(2019/02/03)
-
- Cobalt-Catalyzed Regioselective Olefin Isomerization under Kinetic Control
-
Olefin isomerization is a significant transformation in organic synthesis, which provides a convenient synthetic route for internal olefins and remote functionalization processes. The selectivity of an olefin isomerization process is often thermodynamically controlled. Thus, to achieve selectivity under kinetic control is very challenging. Herein, we report a novel cobalt-catalyzed regioselective olefin isomerization reaction. By taking the advantage of fine-tunable NNP-pincer ligand structures, this catalytic system features high kinetic control of regioselectivity. This mild catalytic system enables the isomerization of 1,1-disubstituted olefins bearing a wide range of functional groups in excellent yields and regioselectivity. The synthetic utility of this transformation was highlighted by the highly selective preparation of a key intermediate for the total synthesis of minfiensine. Moreover, a new strategy was developed to realize the selective monoisomerization of 1-alkenes to 2-alkenes dictated by installing substituents on the γ-position of the double bonds. Mechanistic studies supported that the in situ generated Co-H species underwent migratory insertion of double bond/β-H elimination sequence to afford the isomerization product. The less hindered olefin products were always preferred in this cobalt-catalyzed olefin isomerization due to an effective ligand control of the regioselectivity for the β-H elimination step.
- Liu, Xufang,Zhang, Wei,Wang, Yujie,Zhang, Ze-Xin,Jiao, Lei,Liu, Qiang
-
supporting information
p. 6873 - 6882
(2018/05/30)
-
- Unsaturated aldehydes as alkene equivalents in the Diels-Alder reaction
-
A one-pot procedure is described for using α,β-unsaturated aldehydes as olefin equivalents in the Diels-Alder reaction. The method combines the normal electron demand cycloaddition with aldehyde dienophiles and the rhodium-catalyzed decarbonylation of aldehydes to afford cyclohexenes with no electron-with-drawing substituents. In this way, the aldehyde group serves as a traceless control element to direct the cycloaddition reaction. The Diels-Alder reactions are performed in a diglyme solution in the presence of a catalytic amount of boron trifluoride etherate. Subsequent quenching of the Lewis acid, addition of 0.3% of [Rh(dppp)2Cl] and heating to reflux achieves the ensuing decarbonylation to afford the product cyclohexenes. Under these conditions, acrolein, crotonaldehyde and cinnamaldehyde have been reacted with a variety of 1,3-dienes to afford cyclohexenes in overall yields between 53 and 88%. In these transformations, the three aldehydes serve as equivalents of ethylene, propylene and styrene, respectively.
- Taarning, Esben,Madsen, Robert
-
supporting information; experimental part
p. 5638 - 5644
(2009/05/30)
-
- BF3·OEt2 promotes fast, mild, clean and regioselective dehydration of tertiary alcohols
-
BF3·OEt2 in methylene chloride at 25°C for 2 hours or less is shown to be effective for easy conversion of tertiary alcohols into the corresponding thermodynamically most stable alkenes.
- Posner,Shulman-Roskes,Oh,Carry,Green,Clark,Dai,Anjeh
-
p. 6489 - 6492
(2007/10/02)
-