Selective Catalytic B–H Arylation of <i>o</i>-Carboranyl Aldehydes by a Transient Directing Strategy

Zhang, Xiaolei; Zheng, Hongning; Li, Jie; Xu, Fei; Zhao, Jing; Yan, Hong

doi:10.1021/jacs.7b07160

Cited by 159 publications

(42 citation statements)

References 86 publications

(16 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[17] Both mono-a nd di-selectivity were achieved after tuning reaction conditions. [17] Both mono-a nd di-selectivity were achieved after tuning reaction conditions.…”

Section: Catalytic B(45)-diarylationmentioning

confidence: 99%

See 1 more Smart Citation

Transition‐Metal‐Catalyzed Selective Cage B−H Functionalization of o‐Carboranes

Quan

Qiu

Xie

2018

Chemistry A European J

127

View full text Add to dashboard Cite

Carboranes are a class of carbon-boron molecular clusters with unusual thermal and chemical stabilities. They have been proved as very useful building blocks in supramolecular design, optoelectronics, nanomaterials, boron neutron capture therapy agents and organometallic/coordination chemistry. Thus, the functionalization of o-carboranes has received growing interests. Over the past decades, most of the works in this area have been focused on cage carbon functionalization as the weakly acidic cage C-H proton can be readily deprotonated by strong bases. In sharp contrast, selective cage B-H activation/functionalization among chemically very similar ten B-H vertices is very challenging. Considering the differences in electron density of ten cage B-H bonds in o-carborane and the nature of transition metal complexes, we have tackled this selectivity issue by means of organometallic chemistry. Our strategy is as follows: using electron-rich transition metal catalysts for the functionalization of the most electron-deficient B(3,6)-H vertices (bonded to both cage CH vertices); using electron-deficient transition-metal catalysts for the functionalization of relatively electron-rich B(8,9,10,12)-H vertices (with no bonding to both cage CH vertices); and using the combination of directing groups and electrophilic transition metal catalysts for the functionalization of B(4,5,7,11)-H vertices (bonded to only one cage CH vertex). Successful applications of such a strategy result in the preparation of a large variety of cage B-functionalized carboranes in a regioselective and catalytic manner, which are inaccessible by other means. It is believed that as this field progresses, other cage B-functionalized carboranes are expected to be synthesized, and the results detailed in this concept article will further these efforts.

show abstract

“…[17] Both mono-a nd di-selectivity were achieved after tuning reaction conditions. [17] Both mono-a nd di-selectivity were achieved after tuning reaction conditions.…”

Section: Catalytic B(45)-diarylationmentioning

confidence: 99%

“…In a similar manner, another ‐COOH directed Pd‐catalyzed B(4)‐arylation and B(4,5)‐diarylation of carboranyl aldehyde with aryl iodide was very recently reported (Scheme ) . Both mono‐ and di‐selectivity were achieved after tuning reaction conditions.…”

Section: Catalytic Selective Cage B(45711)−h Functionalizationmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Selective Cage B−H Functionalization of o‐Carboranes

Quan

Qiu

Xie

2018

Chemistry A European J

127

View full text Add to dashboard Cite

show abstract

“…The combined organic phase was dried over MgSO 4 , filtered, and the solvent removed under reduced pressure to give 71% of 9,10-(CH 2 =CHCH 2 ) 2 -1,7-(CH 2 =CHCH 2 ) 2 -closo-C 2 B 10 H 8 (145 mg). 13…”

Section: Synthesis and Characterization Of 10mentioning

confidence: 99%

“…7. ATR: ν = 3062 (vs, (C c -H and =CH 2 )), 2972, 2902 (vs, (=CH-and -CH 2 -)), 2592 (vs, (B-H)), 1634 (vs, (C=C)), 995, 978, 692 (s, (=CH)) 13. C{ 1 H} NMR (75.47 MHz, CDCl 3 ) δ: 139.96 (s, CH 2=CHCH 2 ), 112.09 (s, CH 2 =CHCH 2 ), 52.35 (s, C c -H), 21.67 (m, CH 2 =CHCH 2 ).1 H-NMR (300.13 MHz, CDCl 3 ) δ: 5.89 (m, 2H, CH 2 =CHCH 2 ), 4.88 (m, 4H, CH 2 =CHCH 2 ), 4.94 (s, 2H, C c -H), 1.78 (m, 4H, CH 2 =CHCH 2 ).…”

mentioning

confidence: 99%

m-Carborane as a Novel Core for Periphery-Decorated Macromolecules

et al. 2020

View full text Add to dashboard Cite

Closo m-C2B10H12 can perform as a novel core of globular periphery-decorated macromolecules. To do this, a new class of di and tetrabranched m-carborane derivatives has been synthesized by a judicious choice of the synthetic procedure, starting with 9,10-I2-1,7-closo-C2B10H10. The 2a-NPA (sum of the natural charges of the two bonded atoms) value for a bond, which is defined as the sum of the NPA charges of the two bonded atoms, matches the order of electrophilic reaction at the different cluster bonds of the icosahedral o-and m- carboranes that lead to the formation of B-I bonds. As for m-carborane, most of the 2a-NPA values of B-H vertexes are positive, and their functionalization is more challenging. The synthesis and full characterization of dibranched 9,10-R2-1,7-closo-carborane (R = CH2CHCH2, HO(CH2)3, Cl(CH2)3, TsO(CH2)3, C6H5COO(CH2)3, C6H5COO(CH2)3, N3(CH2)3, CH3CHCH, and C6H5C2N3(CH2)3) compounds as well as the tetrabranched 9,10-R2-1,7-R2-closo-C2B10H8 (R = CH2CHCH2, HO(CH2)3) are presented. The X-ray diffraction of 9,10-(HO(CH2)3)2-1,7-closo-C2B10H10 and 9,10-(CH3CHCH)2-1,7-closo-C2B10H10, as well as their Hirshfeld surface analysis and decomposed fingerprint plots, are described. These new reported tetrabranched m-carborane derivatives provide a sort of novel core for the synthesis of 3D radially grown periphery-decorated macromolecules that are different to the 2D radially grown core of the tetrabranched o-carborane framework.

show abstract

“…[11] Very recently, the groups of Shi, [12] Murakami, [13] Bull, [14] Xu and Jin, [15] Zhang, Li and Yan, [16] Hu [17] independently developed transient directing group assisted Pd-catalyzed C-H olefination and arylation.…”

Section: Introductionmentioning

confidence: 99%

Rh‐catalyzed Transient Directing Group Promoted C—H Amidation of Benzaldehydes Utilizing Dioxazolones

2018

View full text Add to dashboard Cite

Transition‐metal catalyzed C—H functionalization of benzaldehydes is of great interest in organic synthesis. Herein, we developed a transient directing group assisted amidation of benzaldehydes catalyzed by rhodium catalyst. With the employment of 10 mol% of 4‐trifluoromethyl aniline, the in situ generated imine groups as the directing group efficiently enable this transformation. By using this protocol, a wide range of benzaldehydes were efficiently converted into the corresponding N‐(2‐formylphenyl)benzamides utilizing dioxazolones as the nitrogen source.

show abstract

Selective Catalytic B–H Arylation of o-Carboranyl Aldehydes by a Transient Directing Strategy

Cited by 159 publications

References 86 publications

Transition‐Metal‐Catalyzed Selective Cage B−H Functionalization of o‐Carboranes

Transition‐Metal‐Catalyzed Selective Cage B−H Functionalization of o‐Carboranes

m-Carborane as a Novel Core for Periphery-Decorated Macromolecules

Rh‐catalyzed Transient Directing Group Promoted C—H Amidation of Benzaldehydes Utilizing Dioxazolones

Contact Info

Product

Resources

About