%0 Journal Article
%A Metzenthin, Tobias
%A Schreiber, André
%A McMullan, Richard K.
%A Koetzle, Thomas F.
%A Mosher, Harry S.
%A Bau, Robert
%D 1997
%T Absolute Configuration of Chiral Ethanol-1-d: Neutron Diffraction
Analysis of the (−)-(1S)-Camphanate Ester of (+)-(R)-Ethanol-1-d
%U https://acs.figshare.com/articles/journal_contribution/Absolute_Configuration_of_Chiral_Ethanol-1-_i_d_i_Neutron_Diffraction_Analysis_of_the_-_1_i_S_i_-Camphanate_Ester_of_-_i_R_i_-Ethanol-1-_i_d_i_/3706539
%R 10.1021/jo970615n.s001
%2 https://acs.figshare.com/ndownloader/files/5797056
%K camphanate
%K CHDRR
%K chiral methylene groups
%K Cu 2
%K ethanol
%K configuration
%K F 2
%K wR
%K space group P 1
%K Ethanol
%K neutron
%K molecule
%K reflection
%K diffraction
%K analysis
%X The absolute configuration of
(+)-ethanol-1-d has been determined to be R by
the single-crystal
neutron diffraction analysis of its (−)-camphanate ester. The
absolute configuration of the (−)-camphanate group, which served as the chiral reference for the neutron
study, was in turn
established to be 1S,4R in an X-ray anomalous
dispersion study of the complex
Cu2(camphanate)4(ethanol)2. These results provide unambiguous
confirmation that the optical rotation of
(R)-ethanol-1-d (positive) is opposite to that of its higher homologs,
(R)-propanol-1-d,
(R)-butanol-1-d, and (R)-neopentanol-1-d (all negative), and demonstrates the
usefulness of neutron diffraction in determining
the absolute configuration of molecules possessing chiral methylene
groups (i.e., molecules of the
type CHDRR‘). Crystallographic details: for the neutron analysis
of (+)-(R)-ethyl-1-d
(−)-(1S)-camphanate: space group P21212
(orthorhombic), a = 6.422(1) Å, b =
21.004(4) Å, c = 9.275(2) Å,
V = 1251.1(7) Å3, Z = 4;
R(F2) = 0.083, and
wR(F2) = 0.075 for 1114
reflections. For the X-ray
analysis of
Cu2(camphanate)4(ethanol)2:
space group P1 (triclinic), a = 11.086(3),
b = 11.244(3), c
= 13.293(4) Å, α = 111.59(2), β = 107.71(2),
and γ = 105.56(3)°, V = 1397.6(7)
Å3, Z = 1; R(F)
=
0.054, wR(F) = 0.058 for 3672
reflections.
%I ACS Publications