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Title: Determination of the absolute configuration of (+)-neopentyl-1-d alcohol by neutron and x-ray diffraction analysis

Abstract

The absolute configuration of (+)-neopentyl-1-d alcohol, prepared by the reduction of 2,2-dimethylpropanol-1-d by actively fermenting yeast, has been determined to be S by neutron diffraction. The neutron study was carried out on the phthalate half ester of neopentyl-1-d alcohol, crystallized as its strychnine salt. The absolute configuration of the (-)-strychninium cation was first determined by an x-ray anomalous dispersion study of its iodide salt. The chiral skeleton of strychnine then served as a reference from which the absolute configuration of the -O-CHD-C(CH[sub 3])[sub 3] group of neopentyl phthalate was determined. Difference Fourier maps calculated from the neutron data showed unambiguously that the -O-CHD-C(CH[sub 3])[sub 3] groups of both independent molecules in the unit cell had the S configuration. This work proves conclusively that the yeast system reduces aldehydes by delivering hydrogen to the re face of the carbonyl group. Crystallographic details: (-)-strychninium (+)-neopentyl-1-d phthalate, space group P2[sub 1] (monoclinic), a = 18.564(6) [angstrom], b = 7.713(2) [angstrom], c = 23.361(8) [angstrom], [beta] = 94.18(4)[degrees], V = 3336.0(5) [angstrom][sup 3], Z = 2 (T = 100 K). Final agreement factors are R(F) = 0.073 for 2768 reflections collected at room temperature (x-ray analysis) and R(F) = 0.144 for 960 reflections collectedmore » at 100 K (neutron analysis). 49 refs., 7 figs., 2 tabs.« less

Authors:
; ;  [1];  [2];  [3]
  1. Univ. of Southern California, Los Angeles, CA (United States)
  2. Stanford Univ., CA (United States)
  3. Brookhaven National Lab., Upton, NY (United States)
Publication Date:
OSTI Identifier:
6701377
DOE Contract Number:  
AC02-76CH00016
Resource Type:
Journal Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America; (United States)
Additional Journal Information:
Journal Volume: 91:26; Journal ID: ISSN 0027-8424
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; ALCOHOLS; MOLECULAR STRUCTURE; YEASTS; BIOLOGICAL PATHWAYS; FERMENTATION; BIOCONVERSION; EUMYCOTA; FUNGI; HYDROXY COMPOUNDS; MICROORGANISMS; ORGANIC COMPOUNDS; PLANTS; 550200* - Biochemistry

Citation Formats

Yuan, H S.H., Stevens, R C, Bau, R, Mosher, H S, and Koetzle, T F. Determination of the absolute configuration of (+)-neopentyl-1-d alcohol by neutron and x-ray diffraction analysis. United States: N. p., 1994. Web. doi:10.1073/pnas.91.26.12872.
Yuan, H S.H., Stevens, R C, Bau, R, Mosher, H S, & Koetzle, T F. Determination of the absolute configuration of (+)-neopentyl-1-d alcohol by neutron and x-ray diffraction analysis. United States. https://doi.org/10.1073/pnas.91.26.12872
Yuan, H S.H., Stevens, R C, Bau, R, Mosher, H S, and Koetzle, T F. Tue . "Determination of the absolute configuration of (+)-neopentyl-1-d alcohol by neutron and x-ray diffraction analysis". United States. https://doi.org/10.1073/pnas.91.26.12872.
@article{osti_6701377,
title = {Determination of the absolute configuration of (+)-neopentyl-1-d alcohol by neutron and x-ray diffraction analysis},
author = {Yuan, H S.H. and Stevens, R C and Bau, R and Mosher, H S and Koetzle, T F},
abstractNote = {The absolute configuration of (+)-neopentyl-1-d alcohol, prepared by the reduction of 2,2-dimethylpropanol-1-d by actively fermenting yeast, has been determined to be S by neutron diffraction. The neutron study was carried out on the phthalate half ester of neopentyl-1-d alcohol, crystallized as its strychnine salt. The absolute configuration of the (-)-strychninium cation was first determined by an x-ray anomalous dispersion study of its iodide salt. The chiral skeleton of strychnine then served as a reference from which the absolute configuration of the -O-CHD-C(CH[sub 3])[sub 3] group of neopentyl phthalate was determined. Difference Fourier maps calculated from the neutron data showed unambiguously that the -O-CHD-C(CH[sub 3])[sub 3] groups of both independent molecules in the unit cell had the S configuration. This work proves conclusively that the yeast system reduces aldehydes by delivering hydrogen to the re face of the carbonyl group. Crystallographic details: (-)-strychninium (+)-neopentyl-1-d phthalate, space group P2[sub 1] (monoclinic), a = 18.564(6) [angstrom], b = 7.713(2) [angstrom], c = 23.361(8) [angstrom], [beta] = 94.18(4)[degrees], V = 3336.0(5) [angstrom][sup 3], Z = 2 (T = 100 K). Final agreement factors are R(F) = 0.073 for 2768 reflections collected at room temperature (x-ray analysis) and R(F) = 0.144 for 960 reflections collected at 100 K (neutron analysis). 49 refs., 7 figs., 2 tabs.},
doi = {10.1073/pnas.91.26.12872},
url = {https://www.osti.gov/biblio/6701377}, journal = {Proceedings of the National Academy of Sciences of the United States of America; (United States)},
issn = {0027-8424},
number = ,
volume = 91:26,
place = {United States},
year = {1994},
month = {12}
}