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. 2018 Feb 2;20(3):800-803.
doi: 10.1021/acs.orglett.7b03940. Epub 2018 Jan 16.

Challenges in the Conversion of Manual Processes to Machine-Assisted Syntheses: Activation of Thioglycoside Donors with Aryl(trifluoroethyl)iodonium Triflimide

Regis C Saliba  1 , Zachary J Wooke  1 , Gabriel A Nieves  1 , An-Hsiang Adam Chu  2 , Clay S Bennett  2 , Nicola L B Pohl  1   3
Affiliations

Challenges in the Conversion of Manual Processes to Machine-Assisted Syntheses: Activation of Thioglycoside Donors with Aryl(trifluoroethyl)iodonium Triflimide

Regis C Saliba et al. Org Lett. .

Abstract

The steps needed to adapt a stable iodonium promoter for use in automated fluorous-assisted solution-phase oligosaccharide synthesis are described. Direct adaptation of the originally reported batch procedure resulted in the formation of an orthoester or protecting group transfer to the glycosyl acceptor. Fortunately, the addition of inexpensive β-pinene as an acid scavenger avoided both of these side reactions. The utility of this newly developed protocol was applied to the automated solution-phase synthesis of a β-glucan fragment.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Hypervalent iodonium promoters.
Figure 2
Figure 2
Optimization of the reaction conditions. (1) Base = 7 (4 equiv), [2] = 113 mM; (2) base = 7 (4 equiv), [2] = 50 mM; (3) base = 7 (4 equiv), [2] = 15 mM; (4) base = 8 (4 equiv), [2] = 50 mM; (5) base = 8 (4 equiv), [2] = 15 mM; (6) base = 8 (4 equiv), [2] = 5 mM; (7) base = 9 (4 equiv), [2] = 50 mM; (8) base = 10 (4 equiv), [2] = 15 mM; (9) base = 10 (10 equiv), [2] = 15 mM; (10) base = 10 (20 equiv), [2] = 15 mM; (11) no base, [2] = 50 mM; (12) no base, [2] = 15 mM.
Figure 3
Figure 3
Automated solution-phase synthesis of β-1,6-glucan tetramer.
See this image and copyright information in PMC

References

    1. Ley SV, Fitzpatrick DE, Myers RM, Battilocchio C, Ingham RJ. Angew Chem, Int Ed. 2015;54:10122–10136. - PMC - PubMed
    2. Selekman JA, Qiu J, Tran K, Stevens J, Rosso V, Simmons E, Xiao Y, Janey J. Annu Rev Chem Biomol Eng. 2017;8:525–547. - PubMed
    1. Plante OJ, Palmacci ER, Seeberger PH. Science. 2001;291:1523–1527. - PubMed
    2. Plante OJ, Palmacci ER, Seeberger PH. Adv Carbohydr Chem Biochem. 2003;58:35–54. - PubMed
    3. Hahm HS, Schlegel MK, Hurevich M, Eller S, Schuhmacher F, Hofmann J, Pagel K, Seeberger PH. Proc Natl Acad Sci U S A. 2017;114:E3385–E3389. - PMC - PubMed
    4. Geertbeda A, van Mechelen J, Meeuwenoord N, Overkleeft HS, van der Marel GA, Codee JDCJ. Org Chem. 2017;82:12992–13002. - PMC - PubMed
    5. Komba S, Terauchi T, Machida S. J Appl Glycosci. 2009;56:193–206.
    1. Ganesh NV, Fujikawa K, Tan YH, Stine KJ, Demchenko AV. Org Lett. 2012;14:3036–3039. - PMC - PubMed
    2. Pistorio SG, Nigudkar SS, Stine KJ, Demchenko AV. J Org Chem. 2016;81:8796–8805. - PMC - PubMed
    1. Bauer J, Brandenburg K, Zahringer U, Rademann J. Chem -Eur J. 2006;12:7116–7124. - PubMed
    1. Tang SL, Linz LB, Bonning BC, Pohl NL. J Org Chem. 2015;80:10482–10489. - PMC - PubMed
    2. Tang SL, Pohl NL. Org Lett. 2015;17:2642–2645. - PMC - PubMed
    3. Tang SL, Pohl NLB. Carbohydr Res. 2016;430:8–15. - PMC - PubMed

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