15028-39-4

Basic information

• Product Name: H-PHG-OME HCL
• Synonyms: L-PHENYLGLYCINE METHYL ESTER HYDROCHLORIDE;L-PHENYLGLYCINE METHYL ESTER HCL;L-PHENYLGLYCINE METHYL ESTER HYDROCHLORIDE SALT;H-(PH)GLY-OME HCL;H-PHG-OME HCL;(S)-(+)-2-PHENYLGLYCINE METHYL ESTER HYDROCHLORIDE;PHENYLGLYCINE-OME HCL;(S)-(+)-2-phenylglycine methyl ester hydrochlorid
• CAS NO: 15028-39-4
• Molecular Formula: C₉H₁₁NO₂*ClH
• Molecular Weight: 201.65
• EINECS: 1533716-785-6
• Product Categories: Protected Amino Acids;Amino Acids;Peptide Synthesis;Phenylglycine Derivatives;Unnatural Amino Acid Derivatives
• Mol File: 15028-39-4.mol
• Article Data: 45

Chemical Properties

• Melting Point: 200 °C (dec.)(lit.)
• Boiling Point: 238.9°Cat760mmHg
• Flash Point: 104.7°C
• Appearance: /
• Density: g/cm³
• Vapor Pressure: 0.0412mmHg at 25°C
• Storage Temp.: 2-8°C
• CAS DataBase Reference: H-PHG-OME HCL(CAS DataBase Reference)
• NIST Chemistry Reference: H-PHG-OME HCL(15028-39-4)
• EPA Substance Registry System: H-PHG-OME HCL(15028-39-4)

Safety Data

• Hazard Codes: Xi
• Statements: 36
• Safety Statements: 26-36/37
• WGK Germany: 3
• Hazardous Substances Data: 15028-39-4(Hazardous Substances Data)

Usage

Chemical Properties

White to off-white powder

InChI:InChI=1/C9H11NO2.ClH/c1-12-9(11)8(10)7-5-3-2-4-6-7;/h2-6,8H,10H2,1H3;1H/t8-;/m0./s1

Synthetic route

(S)-methyl 2-((S)-1-phenylethylamino)-2-phenylacetate (235786-93-3) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With hydrogenchloride; hydrogen; palladium dihydroxide In methanol under 760.051 Torr; for 15h;	100%
With hydrogenchloride; palladium hydroxide on carbon; hydrogen In methanol; water under 760.051 Torr; for 15h; optical yield given as %ee;	100%

methanol (67-56-1) + (S)-2-phenylglycine (2935-35-5) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With thionyl chloride for 10h; Ambient temperature;	99%
With thionyl chloride for 8h; Heating;	97%
With thionyl chloride In methanol at 20℃; Cooling with ice;	97%

(S)-2-phenylglycine (2935-35-5) + 2,2-dimethoxy-propane (77-76-9) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With hydrogenchloride In water at 20℃;	99%
With hydrogenchloride at 20℃; for 18h;	94%

N-tert-butoxycarbonyl-L-phenylglycine methyl ester (143978-88-5) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With hydrogenchloride In dichloromethane; ethyl acetate at 20℃; for 0.833333h; Inert atmosphere;	97%

methanol (67-56-1) + (S)-α-phenylglycinenitrile (48108-77-6) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With hydrogenchloride	88%
With hydrogenchloride; water	88%

methanol (67-56-1) + (R)-phenylglycine (875-74-1) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + D-phenylglycine methyl ester hydrochloride (19883-41-1)

Conditions	Yield
With thionyl chloride for 20h; Ambient temperature;	A n/a B 76%

N-phthaloylglycine chloride (6780-38-7) + N-benzyliden-α-phenyl-glycine methyl ester (67627-99-0) → C26H20N2O5 + C26H20N2O5 + L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With 2,6-dimethylpyridine In toluene at 20℃; Staudinger Ketene Cycloaddition; Reflux; Inert atmosphere;	A 11% B 4% C 29%

(R)-methyl mandelate (20698-91-3) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + D-phenylglycine methyl ester hydrochloride (19883-41-1)

Conditions	Yield
e.e. = 76percent; Multistep reaction. Title compound not separated from byproducts;

N-benzyliden-α-phenyl-glycine methyl ester (67627-99-0) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + D-phenylglycine methyl ester hydrochloride (19883-41-1)

Conditions	Yield
Product distribution; multistep reaction; deracemisation was investigated by means of dipivaloyltartaric acids of different chirality in the presence of chiral amines of structure Ph-CHCH3-NHR; other temperature, acid, base;
Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts;

N-benzylidenephenylglycine methyl ester (153924-62-0) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + D-phenylglycine methyl ester hydrochloride (19883-41-1)

Conditions	Yield
With (-)-O,O′-di-pivaloyl-L-tartaric acid; lithium (R)-N-methyl-N-α-methylbenzyl amide Product distribution; other lithium amides and diacyltartaric acides;
With (R)-PhCH(CH3)NLiCH2CH3; (3R) HOOCCH(OCOtC4H9)CH(OCOtC4H9)COOH 1.) THF, - 50 deg C; 2.) THF, -70 deg C; Yield given. Multistep reaction. Yields of byproduct given;

methyl N-4'-methoxybenzylidenephenylglycinate (63430-99-9, 88967-39-9, 120328-94-1, 67628-17-5) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + D-phenylglycine methyl ester hydrochloride (19883-41-1)

Conditions	Yield
With (-)-O,O′-di-pivaloyl-L-tartaric acid; lithium diisopropyl amide In tetrahydrofuran; diethyl ether at -105℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

N-<(R)-2-hydroxy-1-phenylethyl>-(S)-2-aminobenzeneacetic acid methyl ester (139225-06-2) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With lead(IV) acetate; hydrogenchloride 1.) CH2Cl2, MeOH, 0 deg C; Yield given. Multistep reaction;

N-paradimethylaminobenzylidene phenylglycinate de methyle (83466-69-7) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + D-phenylglycine methyl ester hydrochloride (19883-41-1)

Conditions	Yield
Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts;

(R) N-benzylidene phenylglycinate de methyle (63903-05-9) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + D-phenylglycine methyl ester hydrochloride (19883-41-1)

Conditions	Yield
Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts;

benzaldehyde (100-52-7) + SASRIN-maleidobenzoic acid resin → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
Multi-step reaction with 4 steps 1: Na2SO4 / methanol / 24 h / 20 °C 2: LiClO4 / acetonitrile / 20 °C 3: 91 percent / ceric ammonium nitrate / acetonitrile; H2O / 4 h / 20 °C 4: 88 percent / HCl View Scheme

[(S)-1-(4-Methoxy-phenyl)-ethyl]-[1-phenyl-meth-(E)-ylidene]-amine (228090-73-1) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
Multi-step reaction with 3 steps 1: LiClO4 / acetonitrile / 20 °C 2: 91 percent / ceric ammonium nitrate / acetonitrile; H2O / 4 h / 20 °C 3: 88 percent / HCl View Scheme

(S)-[(S)-1-(4-Methoxy-phenyl)-ethylamino]-phenyl-acetonitrile (827308-21-4) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: 91 percent / ceric ammonium nitrate / acetonitrile; H2O / 4 h / 20 °C 2: 88 percent / HCl View Scheme

DL-2-phenylglycine methyl ester hydrochloride (15028-40-7) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) Et3N 2.) 3 Angstroem molecular sieves / 1.) Et2O, room temp., 1 h 2.) Et2O, room temp., 48 h View Scheme

phenylglycin (2835-06-5) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
Multi-step reaction with 3 steps 1: 95 percent / SOCl2 / 2 h at 45 deg C, 2 h at room temp. 2: 1.) Et3N 2.) 3 Angstroem molecular sieves / 1.) Et2O, room temp., 1 h 2.) Et2O, room temp., 48 h View Scheme

benzaldehyde (100-52-7) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
Multi-step reaction with 4 steps 1: CHCl3 / 1 h / Ambient temperature; other aldehydes 2: methanol / 8 h / Ambient temperature 3: HCl / methanol / 5 h / Ambient temperature 4: 1.) Pb(OAc)4, 2.) dil. HCl / 1.) CH2Cl2, MeOH, 0 deg C View Scheme

β-[(phenylmethylene)amino]-[R-(E)-]-benzeneethanol (153924-63-1) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
Multi-step reaction with 3 steps 1: methanol / 8 h / Ambient temperature 2: HCl / methanol / 5 h / Ambient temperature 3: 1.) Pb(OAc)4, 2.) dil. HCl / 1.) CH2Cl2, MeOH, 0 deg C View Scheme

N-<(R)-2-hydroxy-1-phenylethyl>-(S)-α-aminobenzeneacetonitrile (139224-87-6) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: HCl / methanol / 5 h / Ambient temperature 2: 1.) Pb(OAc)4, 2.) dil. HCl / 1.) CH2Cl2, MeOH, 0 deg C View Scheme

DL-2-phenylglycine methyl ester hydrochloride (15028-40-7) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + D-phenylglycine methyl ester hydrochloride (19883-41-1)

Conditions	Yield
With sodium hexaflorophosphate; 1,3,5-Tris{[(S,S)-4,5-diphenyl-2-oxazolinyl]methyl}-2,4,6-triethylbenzene In water-d2; chloroform-d1 at 25℃; Resolution of racemate; optical yield given as %ee;
With chiral stationary phase including (R)-naphthylethyl-carbamate-functionalized CF6 In ethanol; n-heptane; trifluoroacetic acid at 20℃; Purification / work up;

[(S)-1-(4-Methoxy-phenyl)-ethyl]-[1-phenyl-meth-(E)-ylidene]-amine (160460-40-2) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
Multi-step reaction with 3 steps 1: lithium perchlorate / acetonitrile / 20 °C 2: 2,3-dicyano-5,6-dichloro-p-benzoquinone / dichloromethane / 20 °C / aq. phosphate buffer 3: hydrogenchloride; water View Scheme

(S)-methyl 2-(benzyloxycarbonylamino)-2-phenylacetate (147780-61-8) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With hydrogenchloride; hydrogen; acetic acid In water

methanol (67-56-1) + (2S)-2-amino-3-(3-nitrophenyl)propanoic acid (19883-74-0) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With thionyl chloride at 20℃; Cooling with ice;

methanol (67-56-1) + (2S)-2-[(tert-butoxycarbonyl)amino]-2-phenylethanoic acid (2900-27-8) → L-2-phenylglycine methyl ester hydrochloride (15028-39-4)

Conditions	Yield
With thionyl chloride at 0 - 23℃; Inert atmosphere;

2,2-dimethyl-4-pentenal (5497-67-6) + L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → (S)-methyl-2-(2,2-dimethyl-pent-4-enylideneamino)-2-phenylacetate

Conditions	Yield
Stage #1: L-2-phenylglycine methyl ester hydrochloride With triethylamine In dichloromethane at 20℃; for 1h; Stage #2: 2,2-dimethyl-4-pentenal With magnesium sulfate In dichloromethane Further stages.;	100%

L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + (4R,5R)-2,2-dimethyl-5-vinyl-[1,3]dioxolane-4-carbaldehyde (155934-55-7) → (S)-methyl-2-[((4S,5R)-2,2-dimethyl-5-vinyl-[1,3]dioxolan-4-yl)methyleneamino]-2-phenylacetate

Conditions	Yield
Stage #1: L-2-phenylglycine methyl ester hydrochloride With triethylamine In dichloromethane at 20℃; for 1h; Stage #2: (4R,5R)-2,2-dimethyl-5-vinyl-[1,3]dioxolane-4-carbaldehyde With magnesium sulfate In dichloromethane Further stages.;	100%

L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + trifluoroacetic anhydride (407-25-0) → (S)-(+)-2-phenyl-N-(trifluoroacetyl)glycine methyl ester (145513-97-9)

Conditions	Yield
With triethylamine In tetrahydrofuran at -78 - 20℃; for 16h;	100%

C26H44O8 + L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → C35H53NO9

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In 1,2-dichloro-ethane at 0 - 20℃; for 1.16667h;	100%

BOC-glycine (4530-20-5) + L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → Boc-Gly-L-Phg-OMe

Conditions	Yield
With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane	100%

di-tert-butyl dicarbonate (24424-99-5) + L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → N-tert-butoxycarbonyl-L-phenylglycine methyl ester (143978-88-5)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 38h;	99%
Stage #1: L-2-phenylglycine methyl ester hydrochloride With potassium carbonate In water for 1h; Stage #2: di-tert-butyl dicarbonate With guanidine hydrochloride In ethanol at 35 - 40℃; for 0.25h;	91%
Stage #1: L-2-phenylglycine methyl ester hydrochloride With triethylamine In tetrahydrofuran for 0.333333h; Cooling; Stage #2: di-tert-butyl dicarbonate In tetrahydrofuran at 20℃; for 24h;	90%
In 1,4-dioxane for 18h; Ambient temperature; Yield given;
With triethylamine In methanol at 0 - 18℃; for 2h;

pyridine-3-carbonyl chloride hydrochloride (20260-53-1) + L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → N-nicotinylphenylglycine methyl ester (891274-00-3)

Conditions	Yield
With triethylamine In dichloromethane at 0℃;	99%

(1R,2R)-2-(t-butyldiphenylsilyloxy)methyl-1-((1R)-1-methyl(carboxymethyl))cyclopropane + L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → C32H39NO4Si

Conditions	Yield
With 4-methyl-morpholine; benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; benzotriazol-1-ol In N,N-dimethyl-formamide at 0 - 20℃; for 3h;	99%

L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + methylamine (74-89-5) → (S)-2-amino-N-methyl-2-phenylacetamide (129213-83-8)

Conditions	Yield
In water at 10 - 20℃; for 75h;	98%

oxalyl dichloride (79-37-8) + L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → (S)-[((S)-Methoxycarbonyl-phenyl-methyl)-aminooxalyl]-amino)-phenyl-acetic acid methyl ester (851679-73-7)

Conditions	Yield
With triethylamine In tetrahydrofuran at 0℃; for 3h;	98%

L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + Trimethylenediamine (109-76-2) → (2S)-N1-(3-aminopropyl)-2-phenylglycinamide (937716-37-5)

Conditions	Yield
Stage #1: L-2-phenylglycine methyl ester hydrochloride With triethylamine In methanol; diethyl ether Stage #2: Trimethylenediamine at 20℃; for 19h; Further stages.;	98%

L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → (S)-N,N-dideutero-2-phenylglycine

Conditions	Yield
Stage #1: L-2-phenylglycine methyl ester hydrochloride With ammonia; sodium hydroxide In chloroform; water Stage #2: With deuteromethanol	98%

L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → (S)-methyl 2-amino-2-(3-nitrophenyl)acetate (1037088-68-8)

Conditions	Yield
Stage #1: L-2-phenylglycine methyl ester hydrochloride With sulfuric acid; nitric acid at -10 - 20℃; Stage #2: With ammonium hydroxide In water pH=9; Cooling with ice;	97%
Stage #1: L-2-phenylglycine methyl ester hydrochloride With sulfuric acid; nitric acid at 0℃; for 4h; Stage #2: With water; sodium hydrogencarbonate In ethyl acetate at 0℃;	2%

L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → methyl (2S)-amino(cyclohexyl)ethanoate hydrochloride (14328-63-3, 14328-64-4)

Conditions	Yield
With hydrogenchloride; hydrogen In methanol; water at 20℃; under 760.051 Torr; for 24h;	97%

potassium cyanate (590-28-3) + L-2-phenylglycine methyl ester hydrochloride (15028-39-4) → (5S)-5-phenyl-2,4-imidazolinedione (27534-88-9)

Conditions	Yield
Stage #1: potassium cyanate; L-2-phenylglycine methyl ester hydrochloride In water Milling; Green chemistry; Stage #2: With caesium carbonate; triethylamine In water Green chemistry;	97%

L-2-phenylglycine methyl ester hydrochloride (15028-39-4) + benzaldehyde (100-52-7) → (benzylidene-amino)-phenyl-acetic acid methyl ester

Conditions	Yield
Stage #1: L-2-phenylglycine methyl ester hydrochloride With triethylamine In dichloromethane for 0.5h; Stage #2: benzaldehyde With magnesium sulfate In dichloromethane	96.8%

Upstream product

• 67-56-1 methanol 
• 2935-35-5 (S)-2-phenylglycine 
• 875-74-1 (R)-phenylglycine 
• 77-76-9 2,2-dimethoxy-propane 
• 235786-93-3 (S)-methyl 2-((S)-1-phenylethylamino)-2-phenylacetate 
• 139225-06-2 N-<(R)-2-hydroxy-1-phenylethyl>-(S)-2-aminobenzeneacetic acid methyl ester 
• 63430-99-9 methyl N-4'-methoxybenzylidenephenylglycinate 
• 6780-38-7 N-phthaloylglycine chloride 
• 67627-99-0 N-benzyliden-α-phenyl-glycine methyl ester 
• 2900-27-8 (2S)-2-[(tert-butoxycarbonyl)amino]-2-phenylethanoic acid 
• 143978-88-5 N-tert-butoxycarbonyl-L-phenylglycine methyl ester 
• 19883-74-0 (2S)-2-amino-3-(3-nitrophenyl)propanoic acid 
• 147780-61-8 (S)-methyl 2-(benzyloxycarbonylamino)-2-phenylacetate 
• 160460-40-2 [(S)-1-(4-Methoxy-phenyl)-ethyl]-[1-phenyl-meth-(E)-ylidene]-amine 

Downstream Products

• 75179-48-5 (S)-((Z)-2-Benzoylamino-3-phenyl-acryloylamino)-phenyl-acetic acid methyl ester 
• 1112971-05-7 N-formyl-L-phenylalanine methyl ester 
• 174635-52-0 (+)-(S)-N-[α-(methoxycarbonyl)benzyl]-2-phenylquinoline-4-carboxamide 
• 851679-73-7 (S)-[((S)-Methoxycarbonyl-phenyl-methyl)-aminooxalyl]-amino)-phenyl-acetic acid methyl ester 
• 266681-40-7 (R)-[((S)-Methoxycarbonyl-phenyl-methyl)-aminooxalyl]-amino)-phenyl-acetic acid benzyl ester 
• 266681-39-4 (R,R)-O,O'-dibenzyl N,N'-oxalylbis(phenylglycine) 
• 283611-27-8 N-(o-nitrobenzenesulfonyl)-L-phenylglycine methyl ester 
• 1027146-29-7 (S)-[(Benzotriazol-1-ylmethyl)-amino]-phenyl-acetic acid methyl ester 
• 696620-23-2 ((S)-3-Benzylamino-2-oxo-3-phenyl-propyl)-phosphonic acid dimethyl ester 
• 797034-78-7 dimethyl (S)-3-[(p-toluenesulfonyl)amino]-2-oxo-3-phenylpropylphosphonate 

Relevant articles and documents

Histone deacetylase 6 inhibitor and preparation method and application thereof

The invention discloses a histone deacetylase 6 inhibitor and a preparation method and application thereof. The histone deacetylase 6 inhibitor has a structure as shown in the following general formula (I). The invention further provides a preparation method of the compound and application of the compound in preparation of drugs for preventing or treating diseases related to HDAC6 activity or abnormal expression.

((S)-3-Mercapto-2-methylpropanamido)acetic acid derivatives as metallo-β-lactamase inhibitors: Synthesis, kinetic and crystallographic studies

The emergence and global spread of metallo-β-lactamase (MBL) mediated resistance to almost all β-lactam antibacterials poses a serious threat to public health. Since no clinically useful MBL inhibitors have been reported, there is an urgent need to develop new potent broad-spectrum MBL inhibitors effective against antibacterial resistance. Herein, we synthesized a set of 2-substituted ((S)-3-mercapto-2-methylpropanamido) acetic acid derivatives, some of which displayed potent inhibition with high ligand efficiency to the clinically relevant MBL subtypes, Verona Integron-encoded MBL (VIM)-2 and New Delhi MBL (NDM)-1. Kinetic studies revealed that the inhibitors are not strong zinc chelators in solution, and they bind reversibly to VIM-2 but dissociate very slowly. Crystallographic analyses revealed that they inhibit VIM-2 via chelating the active site zinc ions and interacting with catalytically important residues. Further cell- and zebrafish-based assays revealed that the inhibitors slightly increase susceptibility of E. coli cells expressing VIM-2 to meropenem, and they have no apparent toxicity to the viability of HEK293T cells and the zebrafish embryogenesis.

Distal Stereocontrol Using Guanidinylated Peptides as Multifunctional Ligands: Desymmetrization of Diarylmethanes via Ullman Cross-Coupling

We report the development of a new class of guanidine-containing peptides as multifunctional ligands for transition-metal catalysis and its application in the remote desymmetrization of diarylmethanes via copper-catalyzed Ullman cross-coupling. Through design of these peptides, high levels of enantioinduction and good isolated yields were achieved in the long-range asymmetric cross-coupling (up to 93:7 er and 76% yield) between aryl bromides and malonates. Our mechanistic studies suggest that distal stereocontrol is achieved through a Cs-bridged interaction between the Lewis-basic C-terminal carboxylate of the peptides with the distal arene of the substrate.