Degradable polymers of a cyclic silyl ether and uses thereof
AssigneeMassachusetts Institute of Technology
InventorsJeremiah A. Johnson, Peyton Shieh, Wenxu Zhang
Life of this patent
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Abstract
The present disclosure provides cyclic silyl ethers of the formula: and salts thereof. The cyclic silyl ethers may be useful as monomers for preparing polymers. Also described herein are polymers prepared by polymerizing a cyclic silyl ether and optionally one or more additional monomers. The polymers may be degradable (e.g., biodegradable). One or more O—Si bonds of the polymers may be the degradation sites. Also described herein are compositions and kits including the cyclic silyl ethers or polymers; methods of preparing the polymers; and methods of using the polymers, compositions, and kits.
Claims26
1-69. (canceled)
A brush-arm star polymer (BASP) prepared by a method comprising crosslinking one or more instances of a brush polymer of in the presence of:
- a crosslinker;
- and
- a metathesis catalyst;
- wherein the brush polymer is prepared by a method comprising polymerizing:
- one or more instances of a first monomer, wherein each instance of the first monomer is independently of Formula (A1) or (A2):
- or a salt thereof;
- and
- a second monomer, where the second monomer is a compound of Formula (B):
- or a salt thereof;
- in the presence of a metathesis catalyst;
- wherein:
- each instance of
- is Ring B, wherein each instance of Ring B is independently a substituted or unsubstituted, monocyclic carbocyclic ring, substituted or unsubstituted, monocyclic heterocyclic ring, substituted or unsubstituted, monocyclic aryl ring, or substituted or unsubstituted, monocyclic heteroaryl ring;
- each instance of Z is independently C(RP)2 or O;
- each instance of RP is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;
- each instance of is independently a single bond or double bond;
- each instance of L1, L2, L3a, and L3b is independently a single bond, substituted or unsubstituted, C1-200 alkylene, substituted or unsubstituted, C2-200 alkenylene, substituted or unsubstituted, C2-200 alkynylene, substituted or unsubstituted, C2-200 heteroalkylene, substituted or unsubstituted, C2-200 heteroalkenylene, or C2-200 heteroalkynylene;
- each instance of R1, R2, R3, and R4 is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl, or two instances of R1 attached to the same carbon atom are taken together to form oxo, or two instances of R2 attached to the same carbon atom are taken together to form oxo, or two instances of R3 attached to the same carbon atom are taken together to form oxo, or two instances of R4 attached to the same carbon atom are taken together to form oxo;
- each instance of W1 and W2 is independently a single bond,
- each instance of RL is independently hydrogen, a nitrogen protecting group when attached to a nitrogen atom, or -L(M)m;
- each instance of M is independently hydrogen or an agent;
- each instance of m is independently an integer between 1 and 10, inclusive;
- each instance of L is independently substituted or unsubstituted, C1-200 alkylene, substituted or unsubstituted, C2-200 alkenylene, substituted or unsubstituted, C2-200 alkynylene, substituted or unsubstituted, C2-200 heteroalkylene, substituted or unsubstituted, C2-200 heteroalkenylene, or substituted or unsubstituted, C2-200 heteroalkynylene;
- optionally one or more carbon atoms in each instance of the substituted or unsubstituted, C1-200 alkylene, substituted or unsubstituted, C2-200 alkenylene, substituted or unsubstituted, C2-200 alkynylene, substituted or unsubstituted, C2-200 heteroalkylene, substituted or unsubstituted, C2-200 heteroalkenylene, and substituted or unsubstituted, C2-200 heteroalkynylene are independently replaced with substituted or unsubstituted carbocyclylene, substituted or unsubstituted heterocyclylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene;
- optionally one or more heteroatoms in each instance of the substituted or unsubstituted, C2-200 heteroalkylene, substituted or unsubstituted, C2-200 heteroalkenylene, and substituted or unsubstituted, C2-200 heteroalkynylene are independently replaced with substituted or unsubstituted carbocyclylene, substituted or unsubstituted heterocyclylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene;
- each instance of e and f is independently an integer between 0 and 10, inclusive;
- each instance of X1 and X2 is independently hydrogen, substituted or unsubstituted, C1-1000 alkyl, substituted or unsubstituted, C2-1000 alkenyl, substituted or unsubstituted, C2-1000 alkynyl, substituted or unsubstituted, C1-1000 heteroalkyl, substituted or unsubstituted, C2-1000 heteroalkenyl, substituted or unsubstituted, C2-1000 heteroalkynyl, —ORC, —N(RC)2, —C(═O)RC, —C(═O)ORC, —C(═O)N(RC)2, —NRCC(═O)RC, —NRCC(═O)ORC, —NRCC(═O)N(RC)2, —OC(═O)RC, —OC(═O)ORC, or —OC(═O)N(RC)2;
- each instance of RC is independently hydrogen, substituted or unsubstituted, C1-1000 alkyl, substituted or unsubstituted, C2-1000 alkenyl, substituted or unsubstituted, C2-1000 alkynyl, substituted or unsubstituted, C1-1000 heteroalkyl, substituted or unsubstituted, C2-1000 heteroalkenyl, substituted or unsubstituted, C2-1000 heteroalkynyl, a leaving group, an oxygen protecting group when attached to an oxygen atom, a nitrogen protecting group when attached to a nitrogen atom,
- each instance of n is independently an integer between 1 and 300, inclusive;
- each instance of RF is independently hydrogen, substituted or unsubstituted, C1-6 alkyl, or an oxygen protecting group;
- or
- is hydrogen or absent, as valency permits;
- Y is O or C(RQ)2;
- each instance of RQ is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;
- each instance of RK is independently hydrogen, halogen, substituted or unsubstituted, C1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —ORN;
- each instance of RN is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or an oxygen protecting group;
- j is 1, 2, or 3;
- and
- k is 0, 1, 2, or 3.
77-87. (canceled)
90-91. (canceled)
(canceled)
97-98. (canceled)
(canceled)
Dependencies are inferred from the claim text.