Page 9 of 12
Journal of the American Chemical Society
Dr. Petra Lindovská, Dr. Olga Mukhina, and Mr. Kyan A.
D’Angelo for helpful discussions.
1
Ed. 2015, 54, 3004–3007. (b) Lin, H.-C.; McMahon, T. C.; Patel, A.;
2
3
4
5
6
7
8
9
Corsello, M.; Simon, A.; Xu, W.; Zhao, M.; Houk, K. N.; Garg, N.
K.; Tang, Y. P450-Mediated Coupling of Indole Fragments To Forge
Communesin and Unnatural Isomers. J. Am. Chem. Soc. 2016, 138,
4002–4005.
REFERENCES
(1) (a) Numata, A.; Takahashi, C.; Ito, Y.; Takada, T.; Kawai, K.;
Usami, Y.; Matsumura, E.; Imachi, M.; Ito, T.; Hasegawa, T.
Communesins, Cytotoxic Metabolites of a Fungus Isolated From a
Marine Alga. Tetrahedron Lett. 1993, 34, 2355–2358. (b) Jadulco, R.;
Edrada, R. A.; Ebel, R.; Berg, A.; Schaumann, K.; Wray, V.; Steube,
K.; Proksch, P. New Communesin Derivatives from the Fungus
Penicillium sp. Derived from the Mediterranean Sponge Axinella
verrucosa. J. Nat. Prod. 2004, 67, 78–81. (c) Hayashi, H.;
Matsumoto, H.; Akiyama, K. New Insecticidal Compounds,
Communesins C, D and E, from Penicillium expansum Link MK-57.
Biosci., Biotechnol., Biochem. 2004, 68, 753–756. (d) Andersen, B.;
Smedsgaard, J.; Frisvad, J. C. Penicillium expansum: Consistent
Production of Patulin, Chaetoglobosins, and Other Secondary
Metabolites in Culture and Their Natural Occurrence in Fruit
Products. J. Agric. Food Chem. 2004, 52, 2421–2428. (e) Dalsgaard,
P. W.; Blunt, J. W.; Munro, M. H. G.; Frisvad, J. C.; Christophersen,
C. Communesins G and H, New Alkaloids from the Psychrotolerant
Fungus Penicillium rivulum. J. Nat. Prod. 2005, 68, 258–261. (f) Fan,
Y.-Q.; Li, P.-H.; Chao, Y.-X.; Chen, H.; Du, N.; He, Q.-X.; Liu, K.-C.
Alkaloids with Cardiovascular Effects from the Marine-Derived
Penicillium expansum Y32. Mar. Drugs. 2015, 13, 6489–6504. (g)
For the structurally related perophoramidine, see: Verbitski, S. M.;
Mayne, C. L.; Davis, R. A.; Concepcion, G. P.; Ireland, C. M.
Isolation, Structure Determination, and Biological Activity of a Novel
Alkaloid, Perophoramidine, from the Philippine Ascidian Perophora
namei. J. Org. Chem. 2002, 67, 7124–7126.
(6) (a) Movassaghi, M.; Ahmad, O. K.; Lathrop, S. P. Directed
Heterodimerization: Stereocontrolled Assembly via Solvent-Caged
Unsymmetrical Diazene Fragmentation. J. Am. Chem. Soc. 2011, 133,
13002–13005. (b) Lathrop, S. P.; Kim, J.; Movassaghi, M. Radical-
mediated Dimerization and Oxidation Reactions for the Synthesis of
Complex Alkaloids. Chimia 2012, 66, 389–393. (c) Lathrop, S. P.;
Movassaghi, M. Application of diazene-directed fragment assembly
to the total synthesis and stereochemical assignment of (+)-
desmethyl-meso-chimonanthine and related heterodimeric alkaloids.
Chem. Sci. 2014, 5, 333–340. (d) Lindovska, P.; Movassaghi, M.
Concise Synthesis of (–)-Hodgkinsine, (–)-Calycosidine, (–)-
Hodgkinsine B, (–)-Quadrigemine C, and (–)-Psycholeine via
Convergent and Directed Modular Assembly of Cyclotryptamines. J.
Am. Chem. Soc., 2017, 139, 17590–17596.
(7) Xie, W.; Jiang, G.; Liu, H.; Hu, J.; Pan, X.; Zhang, H.; Wan, X.;
Lai, Y.; Ma, D. Highly Enantioselective Bromocyclization of
Tryptamines and Its Application in the Synthesis of (–)-
Chimonanthine. Angew. Chem., Int. Ed. 2013, 52, 12924–12927.
(8) The stereochemistry of the epoxide is also implicated in the
observed rate of decomposition. For example, we have found
derivatives containing a (10S)-epoxide to be much more susceptible
to this intramolecular opening than the corresponding (10R)-
derivatives.
(9) For reviews on the synthesis of and asymmetric additions to N-
tert-butanesulfinyl imines, see: (a) Ellman, J. A.; Owens, T. D.; Tang,
T. P. N-tert-Butanesulfinyl Imines: Versatile Intermediates for the
Asymmetric Synthesis of Amines. Acc. Chem. Res. 2002 35, 984–
995. (b) Ferreira, F.; Botuha, C.; Chemla, F.; Pérez-Luna, A. tert-
Butanesulfinimines: structure, synthesis and synthetic applications.
Chem. Soc. Rev. 2009, 38, 1162–1186. (c) Robak, M. T.; Herbage, M.
A.; Ellman, J. A. Synthesis and Applications of tert-
Butanesulfinamide. Chem. Rev. 2010, 110, 3600–3740. For general
reviews of asymmetric additions to N-sulfinyl imines, see: (d) Davis,
F. A.; Zhou, P.; Chen, B.-C. Asymmetric synthesis of amino acids
using sulfinimines (thiooxime S-oxides). Chem. Soc. Rev. 1998, 27,
13–18. (e) Zhou, P.; Chen. B.-C.; Davis, F. A. Recent advances in
asymmetric reactions using sulfinimines (N-sulfinyl imines).
Tetrahedron 2004, 60, 8003–8030. (f) Senanayake, C. H.;
Krishnamurthy, D.; Lu, Z.-H.; Han, Z.; Gallou, I. Enantiopure
Sulfoxides and Sulfinamides: Recent Developments in Their
Stereoselective Synthesis and Applications to Asymmetric Synthesis.
Aldrichimica Acta 2005, 38, 93–104. (g) Morton, D.; Stockman, R. A.
Chiral non-racemic sulfinimines: versatile reagents for asymmetric
synthesis. Tetrahedron 2006, 62, 8869–8905.
(10) Sun, P.; Weinreb, S. M. tert-Butylsulfonyl (Bus), a New
Protecting Group for Amines. J. Org. Chem. 1997 62, 8604–8608.
(11) (a) Weinreb, S. M.; Demko, D. M.; Lessen, T. A.; Demers, J. P.
β-Trimethylsilylethanesulfonyl chloride (SES-Cl): A new reagent for
protection of amines. Tetrahedron Lett. 1986 27, 2099–2102. (b)
Ribière, P.; Declerck, V.; Martinez, J.; Lamaty, F. 2-
(Trimethylsilyl)ethanesulfonyl (or SES) Group in Amine Protection
and Activation. Chem. Rev. 2006, 106, 2249–2269.
(12) For relevant studies on the use of (–)-diacetone-D-glucose
(DAG) as a chiral controller for the preparation of chiral sulfoxides
and sulfinamides, see: (a) Llera, J. M.; Fernández, I.; Alcudia, F. An
efficient synthesis of both enantiomers of chiral non racemic
methylsulfoxides from DAG. Tetrahedron Lett. 1991, 32, 7299–7302.
(b) Fernández, I.; Khiar, N.; Llera, J. M.; Alcudia, F. Asymmetric
synthesis of alkane- and arenesulfinates of diacetone-D-glucose
(DAG): an improved and general route to both enantiomerically pure
sulfoxides. J. Org. Chem. 1992, 57, 6789–6796. (c) Khiar, N.;
Fernández, I.; Alcudia, F. Asymmetric synthesis of optically pure
tert-butyl sulfoxides using the “DAG methodology.” Tetrahedron
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(2) (a) Yang, J.; Wu, H.; Shen, L.; Qin, Y. Total Synthesis of (±)-
Communesin F. J. Am. Chem. Soc. 2007, 129, 13794–13795. (b) Liu,
P.; Seo, J. H.; Weinreb, S. M. Total Synthesis of the Polycyclic
Fungal Metabolite (±)-Communesin F. Angew. Chem., Int. Ed. 2010,
49, 2000–2003. (c) Belmar, J.; Funk, R. L. Total Synthesis of (±)-
Communesin F via a Cycloaddition with Indol-2-one. J. Am. Chem.
Soc. 2012, 134, 16941–16943. (d) Han, S.-J.; Vogt, F.; Krishnan, S.;
May, J. A.; Gatti, M.; Virgil, S. C.; Stoltz, B. M.
A
Diastereodivergent Synthetic Strategy for the Syntheses of
Communesin F and Perophoramidine. Org. Lett. 2014, 16, 3316–
3319. (e) Han, S.-J.; Vogt, F.; May, J. A.; Krishnan, S.; Gatti, M.;
Virgil, S. C.; Stoltz, B. M. Evolution of a Unified, Stereodivergent
Approach to the Synthesis of Communesin F and Perophoramidine. J.
Org. Chem. 2015, 80, 528–547. (f) For a review, see: Trost, B. M.;
Osipov, M. Recent Advances on the Total Synthesis of Communesin
Alkaloids and Perophoramidine. Chem. Eur. J. 2015, 21, 16318–
16343.
(3) (a) Zuo, Z.; Xie, W.; Ma, D. Total Synthesis and Absolute
Stereochemical Assignment of (–)-Communesin F. J. Am. Chem. Soc.
2010, 132, 13226–13228. (b) Lathrop, S. P.; Pompeo, M.; Chang, W.-
T. T.; Movassaghi, M. Convergent and Biomimetic Enantioselective
Total Synthesis of (–)-Communesin F. J. Am. Chem. Soc. 2016, 138,
7763–7769. (c) Liang, X.; Zhang, T.-Y.; Zeng, X.-Y.; Zheng, Y.;
Wei, K.; Yang, Y.-R. Ir-Catalyzed Asymmetric Total Synthesis of (–
)-Communesin F. J. Am. Chem. Soc. 2017, 139, 3364–3367. (d) Park.
J.; Jean, A.; Chen, D. Y.-K. Asymmetric Total Synthesis of
Communesin F and a Putative Member of the Communesin Family.
Angew. Chem., Int. Ed. 2017, 56, 14237–14240. (e) Park, J.; Jean, A.;
Chen, D. Y.-K. Organocatalytic and Late-Stage CH-Functionalization
Enabled Asymmetric Synthesis of Communesin F and Putative
Communesins. J. Org. Chem. 2018, 83, 6936–6957.
(4) Zuo, Z.; Ma, D. Enantioselective Total Syntheses of
Communesins A and B. Angew. Chem., Int. Ed. 2011, 50, 12008–
12011.
(5) (a) Lin, H.-C.; Chiou, G.; Chooi, Y.-H.; McMahon, T. C.; Xu,
W.; Garg, N. K.; Tang, Y. Elucidation of the Concise Biosynthetic
Pathway of the Communesin Indole Alkaloids. Angew. Chem., Int.
9
ACS Paragon Plus Environment