Catalytic Intermolecular C(sp<sup>3</sup>)–H Amination: Selective Functionalization of Tertiary C–H Bonds vs Activated Benzylic C–H Bonds
نویسندگان
چکیده
A catalytic intermolecular amination of nonactivated tertiary C(sp3)–H bonds (BDE 96 kcal·mol–1) is reported for substrates displaying an activated benzylic site 85 kcal·mol–1). The tert...
منابع مشابه
Oxidative functionalization of benzylic C–H bonds by DDQw
C–H activation of the methyl group of toluene and related ArCH3 derivatives by 2,3-dichloro-4,5-dicyano-1,4-benzoquinone (DDQ) gives insertion products, ArCH2O[C6Cl2(CN)2]OH via a rate-determining hydride abstraction by DDQ. The resulting benzylic ether can undergo reactions with phosphines to give benzylic phosphonium salts (Wittig reagents) and with phosphites to give phosphonate esters (Horn...
متن کامل6 Analysis of H – AHn and CH 3 – AHn bonds
Along the series of H–AHn bonds, with AHn = CH3, NH2, OH, and F, the bond dissociation energies show a steady increase as can be expected from the increasing difference in electronegativity along this series. However, in the same series for CH3– AHn the bond strength first decreases from CH3–CH3 to CH3–NH2 and only thereafter increases again along CH3–NH2, CH3–OH and CH3–F. To understand the or...
متن کاملThe origin of the generalized anomeric effect: possibility of CH/n and CH/pi hydrogen bonds.
Ab initio MO calculations were carried out at the MP4/6-311++G(3df,3pd)//MP2/6-311++G(3df,3pd) level to investigate the conformational Gibbs energy of a series of methyl ethers CH(3)O-CH(2)-X (X=OH, OCH(3), F, Cl, Br, CN, C triple bond CH, C(6)H(5), CHO). It was found that the Gibbs energy of the gauche conformers is lower in every case than that of the corresponding anti conformers. In the mor...
متن کامل7 Activation of H – AHn and CH 3 – AHn bonds
We have studied the palladium oxidative insertion reactions into a series of model bonds across the second period, that is, the H–AHn and CH3–AHn bonds, where AHn = CH3, NH2, OH, and F. We investigate what effect this series of increasingly polar bonds has on their intrinsic barriers upon activation by palladium. Our activation strain analyses show nicely how the observed trends are strongly in...
متن کاملCH...O hydrogen bonds at protein-protein interfaces.
For the first time, a statistical potential has been developed to quantitatively describe the CH.O hydrogen bonding interaction at the protein-protein interface. The calculated energies of the CH.O pair interaction show a favorable valley at approximately 3.3 A, exhibiting a feature typical of an H-bond and similar to the ab initio quantum calculation result (Scheiner, S., Kar, T., and Gu, Y. (...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
ژورنال
عنوان ژورنال: Journal of the American Chemical Society
سال: 2021
ISSN: ['0002-7863', '1520-5126', '1943-2984']
DOI: https://doi.org/10.1021/jacs.1c03872