TORABI KOHLBOUNI ET AL.
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centers: a novel approach to the absolute configuration of 1,2-
and 1,3-diols. Angew Chem Int Ed Engl. 2001;40(2):451-454.
10. Scafato P, Superchi S. Biphenyl dioxolanes as circular dichro-
ism probes for the assignment of absolute configuration to ali-
phatic diols: extending the scope to anti 1,n-diols and cyclic
syn 1,2-diols. Chirality. 2010;22(Suppl 1):E3-E10.
11. Tartaglia S, Pace F, Scafato P, Rosini C. A new case of induced
helical chirality in a bichromophoric system: absolute configu-
ration of transparent and flexible diols from the analysis of the
electronic circular dichroism spectra of the corresponding
di(1-naphthyl)ketals. Org Lett. 2008;10:3421-3424.
12. Di Bari L, Pescitelli G, Pratelli C, Pini D, Salvadori P. Determi-
nation of absolute configuration of acyclic 1,2-diols with
Mo2(OAc)4. 1. Snatzke's method revisited. J Org Chem. 2001;66
(14):4819-4825.
13. Li XY, Tanasova M, Vasileiou C, Borhan B. Fluorinated por-
phyrin tweezer: a powerful reporter of absolute configuration
for erythro and threo diols, amino alcohols, and diamines.
J Am Chem Soc. 2008;130:1885-1893.
4 | CONCLUSION
An operationally simple and microscale method for the
absolute stereochemical determination of 1,2-diols is
presented. In situ derivatization with DBA results in the
induced helicity of the two naphthyl substituents, which
leads to an observable ECCD spectrum. The observed
P or M helicity follows a predictable trend for S and
R chiral 1,2-diols, respectively. Predictions for the sign of
the ECCD couplet is derived by assuming a preponder-
ance of either the P or M helicity as a result of minimiz-
ing interactions with the substituents at the asymmetric
center. Computational modeling along with rational pre-
dictions for minimizing steric interactions in a five-
member ring dioxaborolane system yields a mnemonic
that follows the observed trend. Further studies to change
the nature of the chromophore on the boron, not only to
change its absorption profile (bathochromic), but also to
force larger steric interactions, are underway.
14. Zhang J, Gholami H, Ding X, et al. Computationally aided
absolute Stereochemical determination of Enantioenriched
amines. Org Lett. 2017;19(6):1362-1365.
15. Zhang J, Sheng W, Gholami H, Nehira T, Borhan B. Di
(1-naphthyl) methanol ester of carboxylic acids for absolute ste-
reochemical determination. Chirality. 2018;30(2):141-146.
16. Superchi S, Casarini D, Summa C, Rosini C. A general and
nonempirical approach to the determination of the absolute
configuration of 1-aryl-1,2-diols. J Org Chem. 2004;69(5):1685-
1694.
17. Superchi S, Donnoli MI, Rosini C. Determination of the abso-
lute configuration of 1-arylethane-1,2-diols by a nonempirical
analysis of the CD spectra of their 4-biphenylboronates. Org
Lett. 1999;1:2093-2096.
ACKNOWLEDGMENTS
We are grateful to the National Science Foundation
(CHE-1856335) for funding.
ORCID
REFERENCES
18. Gupta AK, Yin X, Mukherjee M, et al. Catalytic asymmetric
epoxidation of aldehydes with two VANOL-derived chiral
borate catalysts. Angew Chem Int Ed Engl. 2019;58(11):3361-
3367.
1. Harada N, Nakanishi K. Circular Dichroic Spectroscopy: Exciton
Coupling in Organic Stereochemistry. Mill Valley, CA: Univer-
sity Science Books; 1983.
2. Harada N, Nakanishi K. A method for determining chiralities
of optically active glycols. J Am Chem Soc. 1969;91:3989-3991.
3. Berova N, Polavarapu PL, Nakanishi K, Woody RW. Compre-
hensive chiroptical spectroscopy, Applications in Stereochemi-
cal Analysis of Synthetic Compounds, Natural Products, and
Biomolecules. Vol.2 Hoboken, NJ: Wiley; 2012.
19. Noth H, Wrackmeyer B. Tables of 11B-NMR Data. Nuclear Mag-
netic Resonance Spectroscopy of Boron Compounds. Berlin:
Springer Verlag; 1978:109-429.
20. Richard J, Birepinte M, Charbonnier JB, Liautard V, Pinet S,
Pucheault M. Borinic acids via direct arylation of amine-borane
complexes: an air- and water -stable boron source. Synthesis.
2017;49:736-744.
4. Lu H, Kobayashi N. Optically active Porphyrin and Phthalocya-
nine systems. Chem Rev. 2016;116:6184-6261.
5. Pasini D, Nitti A. Recent advances in sensing using
atropoisomeric molecular receptors. Chirality. 2016;28(2):
116-123.
6. Wolf C, Bentley KW. Chirality sensing using stereodynamic
probes with distinct electronic circular dichroism output. Chem
Soc Rev. 2013;42(12):5408-5424.
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
7. You L, Zha D, Anslyn EV. Recent advances in Supramolecular
analytical chemistry using optical sensing. Chem Rev. 2015;115:
7840-7892.
8. Berova N, Di Bari L, Pescitelli G. Application of electronic cir-
cular dichroism in configurational and conformational analysis
of organic compounds. Chem Soc Rev. 2007;36(6):914-931.
9. Superchi S, Casarini D, Laurita A, Bavoso A, Rosini C. Induc-
tion of a preferred twist in a biphenyl core by stereogenic
How to cite this article: Torabi Kohlbouni S,
Sarkar A, Zhang J, Li X, Borhan B. Absolute
stereochemical determination of 1,2-diols via
complexation with dinaphthyl borinic acid.