Psychoactive Plant Database - Neuroactive Phytochemical Collection

1. J Phys Chem A. 2008 Aug 28;112(34):7939-46. doi: 10.1021/jp803609m. Epub 2008 
Aug 1.

Synthesis, spectroscopic characterization, and conformational properties of 
trichloromethanesulfenyl acetate, CCl3SOC(O)CH3.

Reina MC(1), Boese R, Ge M, Ulic SE, Beckers H, Willner H, Della Védova CO.

Author information:
(1)CEQUINOR (CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional 
de La Plata, 47 esq. 115, (1900) La Plata, Buenos Aires, República Argentina.

Trichloromethanesulfenyl acetate, CCl 3SOC(O)CH 3, belongs to the family of 
sulfenic esters. This molecule has been characterized by vibrational 
spectroscopy. The conformational and geometrical properties of this species have 
been determined by IR and Raman spectroscopy, X-ray diffraction, and quantum 
chemical calculations. Geometry optimizations of the most stable forms were 
performed with ab initio (HF, MP2) and density functional theory (B3LYP) 
methods. According to our data, this compound results in a gauche-syn conformer 
with C 1 symmetry (gauche orientation around the S-O bond and syn orientation of 
the CO double bond with respect to the S-O single bond) for the most stable 
geometry, and trans-syn conformer with C s symmetry (trans orientation around 
the S-O bond and syn orientation of the CO double bond with respect to the S-O 
single bond) for the second stable conformer (1.1 and 0.53 kcal/mol higher in 
energy than the most stable C 1 form according to the matrix FTIR spectroscopy 
and MP2/6-31G* level of the theory, respectively). The crystalline solid 
(monoclinic, P2 1/ n, a = 8.0152(17) A, b = 5.7922(13) A, c = 17.429(4) A, alpha 
= gamma = 90 degrees , beta = 100.341(3) degrees ) consists exclusively of the 
main form. The geometrical parameters (X-ray diffraction) are d C-Cl = 1.767(19) 
A, d C-S = 1.797(2) A, d S-O = 1.663(14) A, d CO = 1.189(2) A, d O-C = 1.389(3) 
A, d C-C = 1.483(3) A, angles Cl-C-Cl = 110.3(11) degrees , Cl-C-S = 111.8(12) 
degrees , C-S-O = 97.4(8) degrees , S-O-C = 116.7(11) degrees , O-CO = 122.8(19) 
degrees , OC-C = 127.1(2) degrees , and the main torsion angles are delta(CSOC) 
= 105.9(15) degrees and delta(SOC(O)) = 7.6(3) degrees . The geometrical data 
calculated with B3LYP/6-31G++(3df,3pd), B3LYP/6-311G++(3df,3pd), 
B3LYP/aug-cc-pVTZ, and MP2/6-31G* are in good agreement with diffraction data.

DOI: 10.1021/jp803609m
PMID: 18671379


2. J Org Chem. 2006 Nov 24;71(24):9178-82. doi: 10.1021/jo061586w.

Chiral NMR discrimination of piperidines and piperazines using 
(18-crown-6)-2,3,11,12-tetracarboxylic acid.

Lovely AE(1), Wenzel TJ.

Author information:
(1)Department of Chemistry, Bates College, Lewiston, Maine 04240, USA.

Enantiomeric discrimination is observed in the (1)H and (13)C NMR spectra of 
piperidines and piperazines in the presence of 
(-)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. The amines are protonated by 
the carboxylic acid groups of the crown ether to produce the corresponding 
ammonium and carboxylate ions. Association of the ammonium ion with the crown 
ether likely involves two hydrogen bonds with the crown ether oxygen atoms and 
an ion pair with the carboxylate anion. Methyl, hydroxymethyl, phenyl, carboxyl, 
pyridyl, and cyclohexyl substituent groups alpha to the nitrogen atom do not 
inhibit binding of the ammonium ion to the crown ether. The NMR spectra of 
piperidines with the stereogenic center alpha or beta to the nitrogen atom 
exhibit substantial enantiomeric discrimination. Dibasic substrates such as the 
piperizines are likely converted to their diprotonated form in the presence of 
the crown ether, and both nitrogen atoms appear to associate with the crown 
ether moiety.

DOI: 10.1021/jo061586w
PMID: 17109544 [Indexed for MEDLINE]


3. J Org Chem. 2002 Feb 8;67(3):720-5. doi: 10.1021/jo010696u.

Heterodimerization of dye-modified cyclodextrins with native cyclodextrins.

Kuwabara T(1), Aoyagi T, Takamura M, Matsushita A, Nakamura A, Ueno A.

Author information:
(1)Department of Applied Chemistry and Biotechnology, Faculty of Engineering, 
Yamanashi University, 4-3-11 Takeda, Kofu 400-8511, Japan. 
kuwabara@ab11.yamanashi.ac.jp

The heterodimerization behavior of dye-modified beta-cyclodextrins (1-6) with 
native cyclodextrins (CDs) was investigated by means of absorption and induced 
circular dichroism spectroscopy in an aqueous solution. Three types of azo 
dye-modified beta-CDs (1-3) show different association behaviors, depending on 
the positional difference and the electronic character of substituent connected 
to the CD unit in the dye moiety. p-Methyl red-modified beta-CD (1), which has a 
4-(dimethylamino)azobenzene moiety connected to the CD unit at the 4' position 
by an amido linkage, forms an intramolecular self-complex, inserting the dye 
moiety in its beta-CD cavity. It also associates with the native alpha-CD by 
inserting the moiety of 1 into the alpha-CD cavity. The association constants 
for such heterodimerization are 198 M(-1) at pH 1.00 and 305 M(-1) at pH 6.59, 
which are larger than the association constant of 1 for beta-CD (43 M(-1) at pH 
1.00). Methyl red-modified 2, which has the same dye moiety as that for 1 
although its substituent position is different from that of 1, does not 
associate even with alpha-CD due to the stable self-intramolecular complex, in 
which the dye moiety is deeply included in its own cavity of beta-CD. Alizarin 
yellow-modified CD (3), which has an azo dye moiety different from that of 1 and 
2, caused a slight spectral variation upon addition of alpha-CD, suggesting that 
the interaction between 3 and alpha-CD is weak. On the other hand, 
phenolphthalein-modified beta-CD (4), which forms an intermolecular association 
complex in its higher concentrations, binds with beta-CD with an association 
constant of 787 M(-1) at pH 10.80, where 4 exists as the dianion monomer in the 
absence of beta-CD. p-Nitorophenol-modified beta-CDs (5 and 6), each having 
p-nitorophenol moieties with a different connecting part with an amido and 
amidophenyl group, respectively, associated with alpha-CD with association 
constants of 66 and 16 M(-1) for 5 and 6, respectively. The phenyl unit in the 
connecting part of 6 may prevent the smooth binding with alpha-CD. All these 
results suggest that the dye-modified CDs, in which the dye part is not tightly 
included in its CD cavity, associate with the native CD to form heterodimer 
composed of two different CD units by inserting the dye moiety into the native 
CD unit. The resulting heterodimers have a cavity that can bind another 
appending moiety of host molecules. On this basis, more ordered molecular arrays 
or the supramolecular hereropolymers can be constructed.

DOI: 10.1021/jo010696u
PMID: 11856011


4. Inorg Chem. 1997 Jul 16;36(15):3354-3362. doi: 10.1021/ic9700819.

A Bidentate Bisphosphine Functioning in Intramolecular Aliphatic Metalation and 
as an NMR Spectroscopic Probe for the Metal Coordination Environment.

Lesueur W(1), Solari E, Floriani C, Chiesi-Villa A, Rizzoli C.

Author information:
(1)Dipartimento di Chimica, Università di Parma, I-43100 Parma, Italy.

The multistep synthesis of the novel diphosphine reference ligand L(2), 6, 
Ph(2)P(o-C(6)H(4)CH(2)C(6)H(4)-o)PPh(2), has been streamlined and can be 
prepared on a ca. 20 g scale. It forms metallacycles with a variety of metal 
fragments. The resulting, and very rigid, boat-boat conformation forces a proton 
(H(endo)()) of the bridging methylene in close proximity to the metal, which in 
turn renders these protons (H(endo)(), H(exo)()) diastereotopic. The NMR spectra 
of [L(2)MCl(2)] [M = Pd, 9; M = Pt, 10] and of the organometallic derived 
compounds [L(2)Pd(PPh(3))], 11, and [L(2)Pd(Cl)(eta(2)-CH(2)Ph)], 12, consist of 
a pair of doublets, with the H(endo)() coupled to the P of the metallacycle. The 
CH(2)-metal close proximity drives the electrophilic metalation of the bridging 
methylene by RhCl(3) to form [L(2)Rh(Cl)(2)(MeCN)], 13, [L(2) = 
Ph(2)P(o-C(6)H(4)CHC(6)H(4)-o)PPh(2)]. A significant example, which shows how 
the coordination number of the metal can affect the H(exo)()-H(endo)() resonance 
separation, is provided by the couple [L(2)Ni(C(2)H(4))], 14, and 
[L(2)Ni(CO)(2)], 15. In order to show that the metallacycle size is crucial for 
the bridging methylene to function as a spectroscopic probe, we complexed the 
same [Fe(CO)(3)] fragment to L(2), 6, and L'(2), 17, [L'(2) = 
Ph(2)PO(o-C(6)H(2)(4,6Bu(t)(2))CH(2)(4,6Bu(t)(2))C(6)H(2)-o)OPPh(2)], to give 
[L(2)Fe(CO)(3)], 19, and [L'(2)Fe(CO)(3)], 18, respectively. In complex 17 the 
diastereotopic nature of these protons and hence the spectroscopic information 
was lost because of the presence of a 10-membered metallacycle. Crystal data: 9 
is triclinic, space group P&onemacr;, a = 11.987(1) Å, b = 15.990(2) Å, c = 
10.872(1) Å, alpha = 91.42(1) degrees, beta = 111.01(2) degrees, gamma = 
99.86(2) degrees, V = 1908.2(5) Å(3), Z = 2, and R = 0.053; 11 is monoclinic, 
space group C2/c, a = 39.071(5) Å, b = 13.657(4) Å, c = 19.848(5) Å, beta = 
92.45(2) degrees, V = 10581(5) Å(3), Z = 8, and R = 0.047; 12 is triclinic, 
space group P&onemacr;, a = 11.289(1) Å, b = 18.769(2) Å, c = 11.077(1) Å, alpha 
= 91.20(1) degrees, beta = 111.27(1) degrees, gamma = 105.26(1) degrees, V = 
2107.7(4) Å(3), Z = 2, and R = 0.039; 13 is orthorhombic, space group 
P2(1)2(1)2(1), a = 15.346(2) Å, b = 18.188(3) Å, c = 12.072(2) Å, V = 3369.5(9) 
Å(3), Z = 4, and R = 0.042.

DOI: 10.1021/ic9700819
PMID: 11670002


5. Inorg Chem. 1996 Apr 24;35(9):2558-2567. doi: 10.1021/ic9512035.

Molecular Assemblies Containing Unsupported 
[Fe(III)-(&mgr;(2):eta(2)-RCO(2))-Cu(II)] Bridges.

Scott MJ(1), Goddard CA, Holm RH.

Author information:
(1)Department of Chemistry, Harvard University, Cambridge, Massachusetts 02138.

Formate is an inhibitor of cytochrome oxidases and also effects conversion of 
the bovine heart enzyme from the "fast" to the "slow" cyanide-binding form. The 
molecular basis of these effects is unknown; one possibility is that formate 
inserts as a bridge into the binuclear heme a(3)-Cu(B) site, impeding the 
binding of dioxygen or cyanide. Consequently, Fe-Cu-carboxylate interactions are 
a matter of current interest. We have initiated an examination of such 
interactions by the synthesis of the first examples of 
[Fe(III)-(&mgr;(2):eta(2)-RCO(2))-Cu(II)] bridges, minimally represented by 
Fe(III)-L + Cu(II)-O(2)CR --> [Fe(III)-(RCO(2))-Cu(II)] + L. A series of Cu(II) 
precursor complexes and solvate forms have been prepared and their structures 
determined, including [Cu(Me(5)dien)(O(2)CH)](+) (3), 
[Cu(Me(5)dien)(O(2)CH)(MeOH)](+) (4), [Cu(Me(6)tren)(O(2)CH)](+) (5), and 
[Cu(Me(5)dien)(OAc)](+) (6). [4](ClO(4)) was obtained in monoclinic space group 
P2(1)/n with a = 8.166(3) Å, b = 15.119(5) Å, c = 15.070(4) Å, beta = 104.65(2) 
degrees, and Z = 4. [5](ClO(4))/[6](ClO(4)) crystallize in orthorhombic space 
groups Pnma/Pna2(1) with a = 16.788(2)/14.928(5) Å, b = 9.542(1)/9.341(4) Å, c = 
12.911(1)/12.554(4) Å, and Z = 4/4. In all cases, the carboxylate ligand is 
terminal and is bound in a syn orientation. Also prepared for the purpose of 
structural comparison was [Fe(OEP)(O(2)CH)], which occurred in monoclinic space 
group P2(1)/c with a = 13.342(2) Å, b = 13.621(2) Å, c = 19.333(2) Å, beta = 
106.12(2) degrees, and Z = 4. The desired bridges were stabilized in the 
assemblies [(OEP)Fe(O(2)CH)Cu(Me(5)dien)(OClO(3))](+) (9), 
[(OEP)Fe(OAc)Cu(Me(5)dien)](2+) (10), and 
{(OEP)Fe[(O(2)CH)Cu(Me(6)tren)](2)}(3+) (11), which were prepared by the 
reaction of 3, 6, and 5, respectively, with [Fe(OEP)(OClO(3))] in acetone or 
dichloromethane. [9](ClO(4))/[10](ClO(4))(2).CH(2)Cl(2) crystallize in triclinic 
space group P&onemacr; with a = 9.016(3)/13.777(3) Å, b = 15.377(5)/13.847(3) Å, 
c = 19.253(5)/17.608(4) Å, alpha = 78.12(3)/96.82(3) degrees, beta = 
86.30(4)/108.06(3) degrees, gamma = 76.23(3)/114.32(3) degrees, and Z = 2/2. 
Each assembly contains a [Fe(III)-(RCO(2))-Cu(II)] bridge but with the differing 
orientations anti-anti (9) and syn-anti (10, 11). The compound 
[11](ClO(4))(2)(SbF(6)) occurs in orthorhombic space group Pbcn with a = 
12.517(6) Å, b = 29.45(1) Å, c = 21.569(8) Å, and Z = 4. Complex 11 is 
trinuclear; the Fe(III) site has two axial formate ligands with bond distances 
indicative of a high-spin configuration. Structural features of 9-11 are 
discussed and are considered in relation to the possible insertion of formate 
into the binuclear sites of two oxidases whose structures were recently 
determined. The present results contribute to the series of molecular assemblies 
with the bridge groups [Fe(III)-X-Cu(II)], X = O(2)(-), OH(-), and RCO(2)(-), 
all with a common high-spin heme, thereby allowing an examination of electronic 
structure as dependent on the bridging atom or group and bridge structure. 
(Me(5)dien = 1,1,4,7,7-pentamethyldiethylenetriamine; Me(6)tren = 
tris(2-(dimethylamino)ethyl)amine; OEP = octaethylporphyrinate(2-).)

DOI: 10.1021/ic9512035
PMID: 11666470