10.1002/chem.201904028
Chemistry - A European Journal
FULL PAPER
(a)
O
Acknowledgements
1. mCPBA, NaHCO3
-20 oC to -10 oC, 45 h
O
O
DBU (0.1 equiv)
O
O
CHCl3, rt, 1 h, 67%
2.Ethylene glycol, toluene
110 oC, 1.5 h
This work was supported by NSFC (21871178, 21702135 and
21871088), and sponsored by “Chenguang Program” (16CG22)
supported by Shanghai Education Development Foundation and
Shanghai Municipal Education Commission. The computation
was performed at ECNU Public Platform for Innovation (001).
We gratefully thank Prof. Yong-Qiang Tu (Shanghai Jiao Tong
University) for helpful suggestions and comments on this manu-
script.
PhS
ent-3l
O
7, 41% (2 steps)
O
H
O
O
O
ref 16
H
O
O
(+)-ricciocarpin A
8
(b)
SPh
O
Raney Ni, NaPH2O2
C7H15
Conflict of interest
O
O
C7H15
O
acetate buffer pH=5.2
EtOH, rt, 0.5 h, 77%
4s
(R)-dodecan-4-olide
The authors declare no conflict of interest.
Scheme 4. Synthetic Applications of Enantioenriched Sulfenylated Products.
Keywords: Thiolation • Divergent synthesis • Functionalized
lactone • Rearrangement • Computational study
Conclusion
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In summary, we have developed a switchable, versatile, and
modular method for the catalytic asymmetric thiolactonization of
homoallylic acids with a chiral Lewis basic selenide and a
Brønsted acid as the co-catalyst. This strategy enabled rapid
formation of a broad range of enantioenriched γ-butyrolactones
and δ-valerolactones with phenylthio groups. Switchable acid-
controlled 6-endo and 5-exo regioselectivite processes were
developed. The calculation results suggest that C–O and C–S
bond formation might occur simultaneously, without formation of
a stable 5a-coordianted thiiranium ion intermediate. The acid-
mediated stereoselective rearrangement of phenylthio-
substituted lactones were explored. Finally, two bioactive natural
products were obtained from the corresponding phenylthio-
substituted lactones, which shows that these reactions are
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synthetically
useful
and
valuable.
Other
divergent
enantioselective synthesis strategies are under investigation by
our group.
Computational methods
All DFT calculations were performed with the Gaussian 16
(Revision A.03) package[18] using the density functional theory
method. Solution-phase relaxed PES scans and geometry
optimizations of all the minima and transition states involved
were carried out at the MN15[19]/6-31G(d)+DCM (IEF-PCM)[20] //
MN15/6-311G(d,p)+DCM (IEF-PCM) level. The keyword “5D”
was used to specify that five d-type orbitals were used for all
elements in the calculations. Frequency calculations at the same
level were performed to validate each structure as either a
minimum or a transition state and to evaluate its zero-point
energy and thermal corrections at 298 K. All discussed energies
were Gibbs free energies unless otherwise specified. Enthalpies
were also given for reference. 3D structure was prepared with
CYLview.[21]
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Experimental Section
Experimental details and spectra can be found in the Supporting
Information. CCDC 1899805 and 1909781 contains the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre.
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