# US 10,246,487 B2 · Azaindoline compounds as granzyme B inhibitors

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- Number: US 10,246,487 B2
- Document ID: US10246487B2
- Status: Granted
- Kind: B2
- Application number: 15/500,781
- Filed: 2015-07-31
- Published: 2017-08-03
- Granted: 2019-04-02
- Earliest claimed: 2014-08-01
- Assignees: viDA Therapeutics Inc.
- Applicants: viDA Therapeutics Inc.
- Inventors: Dale R. Cameron
- Web page: https://patentgrep.com/patent/US10246487B2

## CPC

- C07K 5/101: {the side chain containing 2 to 4 carbon atoms, e.g. Val, Ile, Leu}
- A61K 8/64: Proteins; Peptides; Derivatives or degradation products thereof
- A61K 38/05: Dipeptides
- A61K 38/06: Tripeptides
- A61P 17/00: Drugs for dermatological disorders
- A61Q 7/00: Preparations for affecting hair growth
- C07K 5/0202: {containing the structure -NH-X-X-C(=0)-, X being an optionally substituted carbon atom or a heteroatom, e.g. beta-amino acids}
- C07K 5/06104: {with the first amino acid being acidic}
- C07K 5/0808: {the side chain containing 2 to 4 carbon atoms, e.g. Val, Ile, Leu}
- C07K 5/0812: {and aromatic or cycloaliphatic}
- A61K 38/00: Medicinal preparations containing peptides (peptides containing beta-lactam rings A61K31/00; cyclic dipeptides not having in their molecule any other peptide link than those which form their ring, e.g. piperazine-2,5-diones, A61K31/00; ergot alkaloids of the cyclic peptide type A61K31/48; containing macromolecular compounds having statistically distributed amino acid units A61K31/74; medicinal preparations containing antigens or antibodies A61K39/00; medicinal preparations characterised by the non-active ingredients, e.g. peptides as drug carriers, A61K47/00)
- C07K: PEPTIDES (peptides in foodstuffs A23; obtaining protein compositions for foodstuffs, working-up proteins for foodstuffs A23J; preparations for medicinal purposes A61K; peptides containing beta-lactam rings C07D; cyclic dipeptides not having in their molecule any other peptide link than those which form their ring, e.g. piperazine-2,5-diones, C07D; ergot alkaloids of the cyclic peptide type C07D519/02; macromolecular compounds having statistically distributed amino acid units in their molecules, i.e. when the preparation does not provide for a specific; but for a random sequence of the amino acid units, homopolyamides and block copolyamides derived from amino acids C08G69/00; macromolecular products derived from proteins C08H1/00; preparation of glue or gelatine C09H; single cell proteins, enzymes C12N; genetic engineering processes for obtaining peptides C12N15/00; compositions for measuring or testing processes involving enzymes C12Q; investigation or analysis of biological material G01N33/00)
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61P: SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS

## Abstract

Azaindoline compounds as granzyme B inhibitors, compositions that include the compounds, and methods for using the compounds. Methods for treating cutaneous scleroderma, epidermolysis bullosa, radiation dermatitis, alopecia areata, and discoid lupus erythematosus are provided.

## Claims

### Claim 1

A compound having Formula (I):
or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R1 is a heteroaryl group selected from
(a) 1,2,3-triazolyl, and
(b) 1,2,3,4-tetrazolyl;
n is 1 or 2;
R2a and R2b are independently selected from hydrogen and C1-C6 alkyl;
R2c at each occurrence is independently selected from
(a) hydrogen,
(b) halogen,
(c) C1-C6 alkyl,
(d) —XR11, wherein X is selected from O, C(═O), S, S═O, or S(═O)2,
(e) —C(═O)N(R12)(R13),
(f) —N(R11)(R12)(R13),
(g) —N—C(═O)—R11, and
(h) —N—C(═O)O—R11,
wherein R11, R12, and R13 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 heteroalkyl, C2-C6 alkenyl, C6-C10 aryl, aralkyl, and C3-C10 heteroaryl;
m is 1, 2, or 3;
R3 is selected from
(a) hydrogen,
(b) C1-C4 alkyl optionally substituted with a carboxylic acid, carboxylate, or carboxylate C1-C8 ester group, an amide optionally substituted with an alkylheteroaryl group, or a heteroaryl group;
Z is an acyl group selected from the group
wherein
Y is hydrogen, heterocycle, —NH2, or C1-C4 alkyl;
R4 is selected from
(i) C1-C12 alkyl,
(ii) C1-C6 heteroalkyl optionally substituted with C1-C6 alkyl,
(iii) C3-C6 cycloalkyl,
(iv) C6-C10 aryl,
(v) heterocyclyl,
(vi) C3-C10 heteroaryl,
(vii) aralkyl, and
(viii) heteroalkylaryl;
R5 is heteroaryl or C(═O)—R10,
wherein R10 is selected from
(i) C1-C12 alkyl optionally substituted with C6-C10 aryl, C1-C10 heteroaryl, amino, or carboxylic acid,
(ii) C1-C10 heteroalkyl optionally substituted with C1-C6 alkyl or carboxylic acid,
(iii) C3-C6 cycloalkyl optionally substituted with C1-C6 alkyl, optionally substituted C6-C10 aryl, optionally substituted C3-C10 heteroaryl, amino, or carboxylic acid,
(iv) C6-C10 aryl optionally substituted with C1-C6 alkyl, optionally substituted C6-C10 aryl, optionally substituted C3-C10 heteroaryl, amino, or carboxylic acid,
(v) heterocyclyl,
(vi) C3-C10 heteroaryl,
(vii) aralkyl, and
(viii) heteroalkylaryl.

### Claim 2 (depends on 1)

The compound of claim 1, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R1 is a heteroaryl group selected from
(a) 1,2,3-triazolyl, and
(b) 1,2,3,4-tetrazolyl;
n is 1;
R2a, R2b, and R2c are hydrogen;
R3 is selected from
(a) hydrogen,
(b) C1-C4 alkyl optionally substituted with a carboxylic acid, carboxylate, or carboxylate C1-C8 ester group, an amide optionally substituted with an alkylheteroaryl group, or a heteroaryl group;
Z is an acyl group selected from the group

### Claim 3 (depends on 1)

The compound of claim 1, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R1 is tetrazole or triazole; n is 1; R3 is hydrogen, C1-C4 alkyl substituted with a carboxylic acid or carboxylate group, C1-C4 alkyl substituted with an amide optionally substituted with an alkylheteroaryl group, or a heteroaryl group; and Z is

### Claim 4 (depends on 1)

The compound of claim 1, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R1 is tetrazole or triazole; n is 1; R3 is hydrogen, or C1-C4 alkyl substituted with a carboxylic acid or carboxylate group, an amide optionally substituted with an alkylheteroaryl group, or a heteroaryl group; and Z is
wherein
R4 is selected from
(i) C1-C12 alkyl,
(ii) C3-C6 cycloalkyl,
(iii) C6-C10 aryl, and
(iv) C3-C10 heteroaryl;
R5 is C(═O)—R10, wherein R10 is selected from
(i) C1-C12 alkyl optionally substituted with C6-C10 aryl, C1-C10 heteroaryl, amino, or carboxylic acid,
(ii) C1-C10 heteroalkyl optionally substituted with C1-C6 alkyl or carboxylic acid,
(iii) C3-C6 cycloalkyl optionally substituted with C1-C6 alkyl, optionally substituted C6-C10 aryl, optionally substituted C3-C10 heteroaryl, amino, or carboxylic acid,
(iv) C6-C10 aryl optionally substituted with C1-C6 alkyl, optionally substituted C6-C10 aryl, optionally substituted C3-C10 heteroaryl, amino, or carboxylic acid,
(v) C3-C10 heteroaryl; and
Y is hydrogen, C1-C4 alkyl, or —NH2.

### Claim 5 (depends on 1)

The compound of claim 1 having Formula (II):
or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R1 is a heteroaryl group selected from
(a) 1,2,3-triazolyl, and
(b) 1,2,3,4-tetrazolyl;
R3 is selected from
(a) hydrogen,
(b) C1-C4 alkyl optionally substituted with a carboxylic acid, carboxylate, or carboxylate C1-C8 ester group, an amide optionally substituted with an alkylheteroaryl group, or a heteroaryl group;
R4 is selected from
(i) C1-C12 alkyl,
(ii) C1-C6 heteroalkyl optionally substituted with C1-C6 alkyl,
(iii) C3-C6 cycloalkyl,
(iv) C6-C10 aryl,
(v) heterocyclyl,
(vi) C3-C10 heteroaryl,
(vii) aralkyl, and
(viii) heteroalkylaryl; and
R10 is selected from
(i) C1-C12 alkyl optionally substituted with C6-C10 aryl, C1-C10 heteroaryl, amino, or carboxylic acid,
(ii) C1-C10 heteroalkyl optionally substituted with C1-C6 alkyl or carboxylic acid,
(iii) C3-C6 cycloalkyl optionally substituted with C1-C6 alkyl, optionally substituted C6-C10 aryl, optionally substituted C3-C10 heteroaryl, amino, or carboxylic acid,
(iv) C6-C10 aryl optionally substituted with C1-C6 alkyl, optionally substituted C6-C10 aryl, optionally substituted C3-C10 heteroaryl, amino, or carboxylic acid,
(v) heterocyclyl,
(vi) C3-C10 heteroaryl,
(vii) aralkyl, and
(viii) heteroalkylaryl.

### Claim 6 (depends on 5)

The compound of claim 5, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R10, when defined as C1-C12 alkyl substituted with a carboxylic acid or carboxylate group, is:
—(CH2)n—CO2H, where n is 2, 3, 4, 5, or 6;
optionally wherein one or more single methylene carbons are substituted with a fluoro, hydroxy, amino, C1-C3 alkyl, or C6-C10 aryl group;
optionally wherein one or more single methylene carbons are substituted with two fluoro or C1-C3 alkyl groups;
optionally wherein one or more single methylene carbons are substituted with two alkyl groups that taken together with the carbon to which they are attached form a 3, 4, 5, or 6-membered carbocyclic ring; and
optionally wherein adjacent carbon atoms from an unsaturated carbon-carbon bond or taken form a benzene ring.

### Claim 7 (depends on 5)

The compound of claim 5, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R10, when defined as C3-C6 cycloalkyl substituted with a carboxylic acid or carboxylate group, is:
wherein n is 1, 2, 3, or 4; and optionally, for n=3 or 4, wherein adjacent carbon atoms from an unsaturated carbon-carbon bond.

### Claim 8 (depends on 5)

The compound of claim 5, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R1 is tetrazole or triazole;
R3 is hydrogen; C1-C4 alkyl optionally substituted with a carboxylic acid, carboxylate, or a carboxylate ester group; or C1-C4 alkyl optionally substituted with an amide, which may be optionally substituted with an alkylheteroaryl group;
R4 is C1-C12 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, C3-C10 heteroaryl, or heterocyclyl; and
R10 is C1-C12 alkyl optionally substituted with C6-C10 aryl, C1-C10 heteroaryl, amino, or carboxylic acid.

### Claim 9 (depends on 5)

The compound of claim 5, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R1 is tetrazole or triazole;
R3 is C1-C4 alkyl optionally substituted with a carboxylic acid, carboxylate, or a carboxylate ester group;
R4 is C1-C8 alkyl or C3-C6 cycloalkyl; and
R10 is selected from:
(a) C1-C3 alkyl substituted with C6-C10 aryl or C1-C10 heteroaryl;
(b) —(CH2)n—CO2H, where n is 2, 3, 4, 5, or 6;
wherein n is 1, 2, 3, or 4.

### Claim 10 (depends on 1)

The compound of claim 1 having Formula (III):
or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein
R1 is a heteroaryl group selected from
(a) 1,2,3-triazolyl, and
(b) 1,2,3,4-tetrazolyl;
R3 is selected from
(a) hydrogen,
(b) C1-C4 alkyl optionally substituted with a carboxylic acid, carboxylate, or carboxylate C1-C8 ester group, an amide optionally substituted with an alkylheteroaryl group, or a heteroaryl group;
Y is hydrogen, heterocycle, —NH2, or C1-C4 alkyl; and
R4 is selected from
(i) C1-C12 alkyl,
(ii) C1-C6 heteroalkyl optionally substituted with C1-C6 alkyl,
(iii) C3-C6 cycloalkyl,
(iv) C6-C10 aryl,
(v) heterocyclyl,
(vi) C3-C10 heteroaryl,
(vii) aralkyl, and
(viii) heteroalkylaryl.

### Claim 11 (depends on 10)

The compound of claim 10, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R1 is tetrazole or triazole;
R3 is hydrogen; C1-C4 alkyl optionally substituted with a carboxylic acid, carboxylate, or a carboxylate ester group; or C1-C4 alkyl optionally substituted with an amide, which may be optionally substituted with an alkylheteroaryl group;
R4 is C1-C12 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, C3-C10 heteroaryl, or heterocyclyl; and
Y is hydrogen, C1-C4 alkyl, or —NH2.

### Claim 12 (depends on 10)

The compound of claim 10, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, wherein:
R1 is tetrazole or triazole;
R3 is C1-C4 alkyl optionally substituted with a carboxylic acid, carboxylate, or a carboxylate ester group;
R4 is selected from
(i) C1-C8 alkyl,
(ii) C3-C6 cycloalkyl,
(iii) C6-C10 aryl,
(iv) C3-C10 heteroaryl, and
(v) heterocyclyl; and
Y is hydrogen.

### Claim 13 (depends on 1)

A compound of claim 1 selected from the group consisting of:
(S)-1-(2-(((2S,3S)-2-(2-(2H-tetrazol-5-yl)acetamido)-3-methylpentanamido)acetyl)-N-((2H-tetrazol-5-yl)methyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine-2-carboxamide;
3-{[(1S,2S)-2-methyl-1-({2-oxo-2-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl]ethyl}carbamoyl)butyl]carbamoyl}propanoic acid;
(S)—N-((1H-1,2,3-triazol-4-yl)methyl)-1-(2-((2S,3S)-3-methyl-2-(2-phenylacetamido)pentanamido)acetyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine-2-carboxamide;
(S)—N-((2H-tetrazol-5-yl)methyl)-1-(2-((2S,3S)-3-methyl-2-(2-phenylacetamido)pentanamido)acetyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine-2-carboxamide;
(S)-5-((S)-2(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((2S,3S)-2-(3-carboxypropanamido)-3-methylpentanamido)-5-oxopentanoic acid;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((2S,3S)-2-acetamido-3-methylpentanamido)-5-oxopentanoic acid;
3-{[(1S,2S)-2-methyl-1-[(2S)-1-oxo-1-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]propan-2-yl]carbamoyl butyl]carbamoyl}propanoic acid;
(3S)-3-[(2S,3S)-2-(3-carboxypropanamido)-3-methylpentanamido]-4-oxo-4-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]butanoic acid;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((S)-2-(3-carboxypropanamido)-2-cyclopentylacetamido)-5-oxopentanoic acid;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((2S,3S)-3-methyl-2-(2-phenylacetamido)pentanamido)-5-oxopentanoic acid;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((S)-3-methyl-2-(2-phenylacetamido)butanamido)-5-oxopentanoic acid;
(S)-5-((S)-2(((1H-1,2,3-triazol-4-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((2S,3S)-2-(3-carboxypropanamido)-3-methylpentanamido)-5-oxopentanoic acid;
(4S)-4-[(2S,3S)-3-methyl-2-[2-(2H-1,2,3,4-tetrazol-5-yl)acetamido]pentanamido]-5-oxo-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(S)-benzyl-5-((S)-2-4(2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((2S,3S)-2-acetamido-3-methylpentanamido)-5-oxopentanoate;
(S)—N-((2H-tetrazol-5-yl)methyl)-1-((S)-2-((2S,3S)-3-methyl-2-(2-phenylacetamido)pentanamido)propanoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine-2-carboxamide;
(2S)-1-[(2R)-2-[(2S,3S)-3-methyl-2-(3-carboxypropanamido)pentanamido]propanoyl]-N-(2H-1,2,3,4-tetrazol-5-ylmethyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine-2-carboxamide;
(S)-6-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-5-((2S,3S)-2-(3-carboxypropanamido)-3-methylpentanamido)-6-oxohexanoic acid;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((S)-2-(3-carboxypropanamido)-3-methylbutanamido)-5-oxopentanoic acid;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((S)-2-cyclopentyl-2-(2-phenylacetamido)acetamido)-5-oxopentanoic acid;
(4S)-4-[(2S)-2-acetamido-3-methylbutanamido]-5-oxo-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((S)-2-amino-3-methylbutanamido)-5-oxopentanoic acid hydrochloride;
(R)-5-((S)-2(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((2S,3S)-2-(3-carboxypropanamido)-3-methylpentanamido)-5-oxopentanoic acid;
4-(((S)-1-(((S)-1-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo [2,3-b]pyridin-1-yl)-5-amino-1,5-dioxopentan-2-yl)amino)-3-methyl-1-oxobutan-2-yl)amino)-4-oxobutanoic acid;
(S)-methyl-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((S)-3-methyl-2-(2-phenylacetamido)butanamido)-5-oxopentanoate;
methyl-(4S)-4-[(2S)-2-acetamido-3-methylbutanamido]-5-oxo-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoate;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-(3-methylbutanamido)-5-oxopentanoic acid;
4-(((S)-1-(((S)-1-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-amino-1,4-dioxobutan-2-yl)amino)-3-methyl-1-oxobutan-2-yl)amino)-4-oxobutanoic acid;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-(2-cyclopentylacetamido)-5-oxopentanoic acid;
(S)-5-((S)-24(2-(2H-tetrazol-5-yl)ethyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((2S,3S)-2-(3-carboxypropanamido)-3-methylpentanamido)-5-oxopentanoic acid;
3-{[(1S,2S)-2-methyl-1-[(2S)-1-oxo-3-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]propan-2-yl]carbamoyl}butyl]carbamoyl}propanoic acid;
(S)-5-((S)-2-(((2H-tetrazol-5-yl)methyl)carbamoyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-1-yl)-4-((2S,3S)-3-methyl-2-(pyrimidin-2-ylamino)pentanamido)-5-oxopentanoic acid;
(4S)-4-(2-cyclohexylacetamido)-5-oxo-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(4S)-5-oxo-4-(2-phenylacetamido)-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(4S)-5-oxo-4-[(2R)-2-phenylpropanamido]-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(4S)-5-oxo-4-[(2S)-2-phenylpropanamido]-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(4S)-4-(2-cyclobutylacetamido)-5-oxo-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(4S)-4-(2-cyclopropylacetamido)-5-oxo-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(4S)-5-oxo-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]-4-[2-(thiophen-3-yl)acetamido]pentanoic acid;
(4S)-4-[2-(morpholin-2-yl)acetamido]-5-oxo-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(4S)-4-[2-(morpholin-3-yl)acetamido]-5-oxo-5-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
(4S)-4-(2-cyclopentylacetamido)-5-oxo-5-[(2S)-2-[(1H-1,2,3-triazol-4-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]pentanoic acid;
3-{[(1S,2S)-2-methyl-1-{[(2S)-1-oxo-3-(2H-1,2,3,4-tetrazol-5-yl)-1-[(2S)-2-[(2H-1,2,3,4-tetrazol-5-ylmethyl)carbamoyl]-1H,2H,3H-pyrrolo[2,3-b]pyridin-1-yl]propan-2-yl]carbamoyl}butyl]carbamoyl}propanoic acid; and
stereoisomers, tautomers, or pharmaceutically acceptable salts thereof.

### Claim 14 (depends on 1)

A pharmaceutical composition, comprising a compound of claim 1, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier.

### Claim 15 (depends on 1)

A method for inhibiting Granzyme B in a subject, comprising administering an effective amount of a compound of claim 1, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, to a subject in need thereof.

### Claim 16 (depends on 1)

A method of treating a condition selected from dissection, aneurysm, and atherosclerosis, comprising administering a therapeutically effective amount of a compound of claim 1, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, to a subject in need thereof.

### Claim 17 (depends on 1)

A method for treating a wound, comprising administering a therapeutically effective amount of a compound of claim 1, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, to a subject in need thereof, wherein administering the compound, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, promotes wound healing.

### Claim 18 (depends on 1)

A method for treating cutaneous scleroderma, epidermolysis bullosa, alopecia areata, or discoid lupus erythematosus, comprising administering a therapeutically effective amount of a compound of claim 1, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, to a subject in need thereof.

### Claim 19 (depends on 18)

The method of claim 18, wherein administering the compound or composition comprises topical administration.