Bridge-Chlorinated Bicyclo[1.1.1]pentane-1,3-dicarboxylic Acids

被引：18

作者：

Kaleta, Jiri ^{[1
,2
]}

Roncevic, Igor ^{[1
]}

Cisarova, Ivana ^{[3
]}

Dracinsky, Martin ^{[1
]}

Solinova, Veronika ^{[1
]}

Kasicka, Vaclav ^{[1
]}

Michl, Josef ^{[1
,2
]}

机构：

[1] Czech Acad Sci, Inst Organ Chem & Biochem, Flemingovo Nam 2, Prague 16610 6, Czech Republic

[2] Univ Colorado, Dept Chem, Boulder, CO 80309 USA

[3] Charles Univ Prague, Fac Sci, Dept Inorgan Chem, Hlavova 2030, Prague 12840 2, Czech Republic

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2019年 / 84卷 / 05期

关键词：

MOLECULAR ROTORS; SURFACE INCLUSION; CAGE COMPOUNDS; STRAIN; ENERGY; ARRAYS; PAIRS; MOTION; RODS;

D O I：

10.1021/acs.joc.8b02780

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Radical chlorination of bicyclo[1.1.1]pentane-1,3-dicarboxylic acid is highly selective, and up to four chlorine atoms can be introduced relatively easily without damage to the strained bicyclic cage. Combined with hydrodechlorination with TMS3SiH, direct chlorination provides access to five of the 15 possible chlorinated diacids. Their configuration has been established by X-ray diffraction. Their pKa values have been measured by capillary electrophoresis and calculated at the B3LYP-D3BJ/6-311+G(d,p)-level. The results are in good agreement and reflect the expected trend, from 2.78 +/- 0.08 and 4.14 +/- 0.10 in the parent to 1.07 +/- 0.03 and 2.31 +/- 0.03 in the tetrachlorinated diacid. Strain energy relative to the parent diacid was calculated for all 15 chlorinated diacids and shows a dramatic increase with successive chlorination, due to nonbonded Cl-Cl repulsions.

引用

页码：2448 / 2461

页数：14

共 53 条

[1] Alabugin I. V., 2016, STEREOELECTRONIC EFF, DOI DOI 10.1002/9781118906378
[2] Gabedit-A Graphical User Interface for Computational Chemistry Softwares
Allouche, Abdul-Rahman
[J]. JOURNAL OF COMPUTATIONAL CHEMISTRY, 2011, 32 (01) : 174 - 182
[3] POLAR SUBSTITUENT EFFECTS IN 1,3-DISUBSTITUTED BICYCLO[1.1.1]PENTANES
APPLEQUIST, DE
RENKEN, TL
WHEELER, JW
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1982, 47 (25) : 4985 - 4995
[4] NEW STRAINED ORGANIC-MOLECULES - THEORY GUIDES EXPERIMENT
BALAJI, V
MICHL, J
[J]. PURE AND APPLIED CHEMISTRY, 1988, 60 (02) : 189 - 194
[5] Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model
Barone, V
Cossi, M
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (11) : 1995 - 2001
[6] Synthesis and applications of highly functionalized 1-halo-3-substituted bicyclo[1.1.1]pentanes
Caputo, Dimitri F. J.
Arroniz, Carlos
Durr, Alexander B.
Mousseau, James J.
Stepan, Antonia F.
Mansfield, Steven J.
Anderson, Edward A.
[J]. CHEMICAL SCIENCE, 2018, 9 (23) : 5295 - 5300
[7] Time-Resolved Fluorescence Anisotropy of Bicyclo[1.1.1]pentane/Tolane-Based Molecular Rods Included in Tris(o-phenylenedioxy)cyclotriphosphazene (TPP)
Cipolloni, Marco
Kaleta, Jiri
Masat, Milan
Dron, Paul I.
Shen, Yongqiang
Zhao, Ke
Rogers, Charles T.
Shoemaker, Richard K.
Michl, Josef
[J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2015, 119 (16) : 8805 - 8820
[8] Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model
Cossi, M
Rega, N
Scalmani, G
Barone, V
[J]. JOURNAL OF COMPUTATIONAL CHEMISTRY, 2003, 24 (06) : 669 - 681
[9] Cottrell T.L., 1958, The Strengths of Chemical Bonds, V2nd
[10] Propellanes-From a Chemical Curiosity to "Explosive" Materials and Natural Products
Dilmac, Alicia M.
Spuling, Eduard
de Meijere, Armin
Braese, Stefan
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (21) : 5684 - 5718

← 1 2 3 4 5 6 →