Journal of the American Chemical Society
Article
́ ́
(23) Sun, S.; Companon, I.; Martínez-Saez, N.; Seixas, J. D.;
̃
(4) Bodanszky, M.; Bednarek, M. A. Experiments on the Protection
of the Thioether in Methionine. Int. J. Pept. Protein Res. 1982, 20,
408−413.
Boutureira, O.; Corzana, F.; Bernardes, G. J. L. Enhanced
Permeability and Binding Activity of Isobutylene-Grafted Peptides.
ChemBioChem 2018, 19, 48−52.
(5) Kleanthous, C.; Coggins, J. R. Reversible Alkylation of an Active
Site Methionine Residue in Dehydroquinase. J. Biol. Chem. 1990, 265,
10935−10939.
(24) Blackwell, H. E.; Sadowsky, J. D.; Howard, R. J.; Sampson, J.
N.; Chao, J. A.; Steinmetz, W. E.; O’Leary, D. J.; Grubbs, R. H. Ring-
Closing Metathesis of Olefinic Peptides: Design, Synthesis, and
Structural Characterization of Macrocyclic Helical Peptides. J. Org.
Chem. 2001, 66, 5291−5302.
(6) Gross, E.; Witkop, B. Nonenzymatic Cleavage of Peptide Bonds -
Methionine Residues in Bovine Pancreatic Ribonuclease. J. Biol.
Chem. 1962, 237, 1856−1860.
(7) Taylor, M. T.; Nelson, J. E.; Suero, M. G.; Gaunt, M. J. A Protein
Functionalization Platform Based on Selective Reactions at
Methionine Residues. Nature 2018, 562, 563−568.
(8) Wang, D.; Yu, M.; Liu, N.; Lian, C.; Hou, Z.; Wang, R.; Zhao,
R.; Li, W.; Jiang, Y.; Shi, X.; Li, S.; Yin, F.; Li, J. A Sulfonium Tethered
Peptide Ligand Rapidly and Selectively Modifies Protein Cysteine in
Vicinity. Chem. Sci. 2019, 10, 4966−4972.
(25) Schafmeister, C. E.; Po, J.; Verdine, G. L. An All-Hydrocarbon
Cross-Linking System for Enhancing the Helicity and Metabolic
Stability of Peptides. J. Am. Chem. Soc. 2000, 122, 5891−5892.
(26) Shi, X.; Zhao, R.; Jiang, Y.; Zhao, H.; Tian, Y.; Jiang, Y.; Li, J.;
Qin, W.; Yin, F.; Li, Z. Reversible Stapling of Unprotected Peptides
via Chemoselective Methionine Bis-Alkylation/Dealkylation. Chem.
Sci. 2018, 9, 3227−3232.
(27) Maity, S. K.; Jbara, M.; Laps, S.; Brik, A. Efficient Palladium-
Assisted One-Pot Deprotection of (Acetamidomethyl)Cysteine
Following Native Chemical Ligation and/or Desulfurization To
Expedite Chemical Protein Synthesis. Angew. Chem., Int. Ed. 2016, 55,
8108−8112.
(28) Jbara, M.; Laps, S.; Morgan, M.; Kamnesky, G.; Mann, G.;
Wolberger, C.; Brik, A. Palladium Prompted On-Demand Cysteine
Chemistry for the Synthesis of Challenging and Uniquely Modified
Proteins. Nat. Commun. 2018, 9, 1−11.
(29) Jbara, M.; Laps, S.; Maity, S. K.; Brik, A. Palladium-Assisted
Cleavage of Peptides and Proteins Containing a Backbone with
Thiazolidine Linkage. Chem. - Eur. J. 2016, 22, 14851−14855.
(30) Stenton, B. J.; Oliveira, B. L.; Matos, M. J.; Sinatra, L.;
Bernardes, G. J. L. A Thioether-Directed Palladium-Cleavable Linker
for Targeted Bioorthogonal Drug Decaging. Chem. Sci. 2018, 9,
4185−4189.
(9) Shen, B. Q.; Xu, K.; Liu, L.; Raab, H.; Bhakta, S.; Kenrick, M.;
Parsons-Reponte, K. L.; Tien, J.; Yu, S. F.; Mai, E.; et al. Conjugation
Site Modulates the in Vivo Stability and Therapeutic Activity of
Antibody-Drug Conjugates. Nat. Biotechnol. 2012, 30, 184−189.
(10) Nischan, N.; Chakrabarti, A.; Serwa, R. A.; Bovee-Geurts, P. H.
M.; Brock, R.; Hackenberger, C. P. R. Stabilization of Peptides for
Intracellular Applications by Phosphoramidate-Linked Polyethylene
Glycol Chains. Angew. Chem., Int. Ed. 2013, 52, 11920−11924.
(11) Bolm, C.; Muller, D.; Dalhoff, C.; Hackenberger, C. P. R.;
̈
Weinhold, E. The Stability of Pseudopeptides Bearing Sulfoximines as
Chiral Backbone Modifying Element towards Proteinase K. Bioorg.
Med. Chem. Lett. 2003, 13, 3207−3211.
(12) Olson, E. J.; Lechtenberg, B. C.; Zhao, C.; De La Torre, E. R.;
Lamberto, I.; Riedl, S. J.; Dawson, P. E.; Pasquale, E. B. Modifications
of a Nanomolar Cyclic Peptide Antagonist for the EphA4 Receptor to
Achieve High Plasma Stability. ACS Med. Chem. Lett. 2016, 7, 841−
846.
(31) Bird, G. H.; Mazzola, E.; Opoku-Nsiah, K.; Lammert, M. A.;
Godes, M.; Neuberg, D. S.; Walensky, L. D. Biophysical Determinants
for Cellular Uptake of Hydrocarbon-Stapled Peptide Helices. Nat.
Chem. Biol. 2016, 12, 845−852.
(32) Zhang, H.; Zhao, Q.; Bhattacharya, S.; Waheed, A. A.; Tong,
X.; Hong, A.; Heck, S.; Curreli, F.; Goger, M.; Cowburn, D.; Freed, E.
O.; Debnath, A. K. A Cell-Penetrating Helical Peptide as a Potential
HIV-1 Inhibitor. J. Mol. Biol. 2008, 378, 565−580.
(13) Spicer, C. D.; Davis, B. G. Selective Chemical Protein
Modification. Nat. Commun. 2014, 5, 1−14.
(14) Hananya, N.; Reid, J. P.; Green, O.; Sigman, M. S.; Shabat, D.
Rapid Chemiexcitation of Phenoxy-Dioxetane Luminophores Yields
Ultrasensitive Chemiluminescence Assays. Chem. Sci. 2019, 10,
1380−1385.
(15) Milo, A.; Neel, A. J.; Toste, F. D.; Sigman, M. S. A Data-
Intensive Approach to Mechanistic Elucidation Applied to Chiral
Anion Catalysis. Science 2015, 347, 737−743.
(16) Neel, A. J.; Milo, A.; Sigman, M. S.; Toste, F. D.
Enantiodivergent Fluorination of Allylic Alcohols: Data Set Design
Reveals Structural Interplay between Achiral Directing Group and
Chiral Anion. J. Am. Chem. Soc. 2016, 138, 3863−3875.
(17) Christian, A. H.; Niemeyer, Z. L.; Sigman, M. S.; Toste, F. D.
Uncovering Subtle Ligand Effects of Phosphines Using Gold(I)
Catalysis. ACS Catal. 2017, 7, 3973−3978.
(18) Niemeyer, Z. L.; Pindi, S.; Khrakovsky, D. A.; Kuzniewski, C.
N.; Hong, C. M.; Joyce, L. A.; Sigman, M. S.; Toste, F. D.
Parameterization of Acyclic Diaminocarbene Ligands Applied to a
Gold(I)-Catalyzed Enantioselective Tandem Rearrangement/Cycliza-
tion. J. Am. Chem. Soc. 2017, 139, 12943−12946.
(19) Harper, K. C.; Sigman, M. S. Three-Dimensional Correlation of
Steric and Electronic Free Energy Relationships Guides Asymmetric
Propargylation. Science 2011, 333, 1875−1878.
(20) Spokoyny, A. M.; Zou, Y.; Ling, J. J.; Yu, H.; Lin, Y. S.;
Pentelute, B. L. A Perfluoroaryl-Cysteine SNAr Chemistry Approach
to Unprotected Peptide Stapling. J. Am. Chem. Soc. 2013, 135, 5946−
5949.
(21) Kubota, K.; Dai, P.; Pentelute, B. L.; Buchwald, S. L. Palladium
Oxidative Addition Complexes for Peptide and Protein Cross-Linking.
J. Am. Chem. Soc. 2018, 140, 3128−3133.
(22) Lau, Y. H.; De Andrade, P.; Quah, S. T.; Rossmann, M.; Laraia,
̈
L.; Skold, N.; Sum, T. J.; Rowling, P. J. E.; Joseph, T. L.; Verma, C.;
̈
Hyvonen, M.; Itzhaki, L. S.; Venkitaraman, A. R.; Brown, C. J.; Lane,
D. P.; Spring, D. R. Functionalised Staple Linkages for Modulating the
Cellular Activity of Stapled Peptides. Chem. Sci. 2014, 5, 1804−1809.
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