Substituted 3-hydroxy-δ-lactones from epoxides

Patent metadata

Field	Value
Publication number	US-9676743-B2
Application number	US-201314017803-A
Country	US
Kind code	B2
Filing date	Sep 4, 2013
Priority date	Nov 20, 2008
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

Abstract

Catalysts and methods for the carbonylation of epoxides to substituted 3-hydroxy-δ-lactones and β-lactones are disclosed.

First claim

We claim:

1. A method comprising steps of:
reacting an epoxide of formula S-Ia′:

wherein:
P′ is hydrogen;
Q′ is selected from the group consisting of: hydrogen; halogen; (a) C 1 to C 20 alkyl; (b) C 2 to C 20 alkenyl; (c) C 2 to C 20 alkynyl; (d) up to a C 16 carbocycle; (e) up to a C 16 heterocycle; and (f) —C(R 13 ) z H (3-z) ; or
wherein the

moiety of S-Ia′ is selected from:

wherein R e at each occurrence is independently selected from the group consisting of: hydrogen; C 1 -C 12 alkyl; C 2 -C 12 alkenyl; C 2 -C 12 alkynyl; aryl; heteroaryl; halogen; —OR 10 ; —OC(O)R 13 ; —OC(O)OR 13 ; —OC(O)NR 11 R 12 ; —CN; —CNO; —C(O)R 13 ; —C(R 13 ) z H (3-z) ; —C(O)OR 13 ; —C(O)NR 11 R 12 ; —NR 11 R 12 ; —NR 11 C(O)R 10 ; —NR 11 C(O)OR 13 ; —NR 11 SO 2 R 13 ; —NCO; —N 3 ; —NO 2 ; —S(O) x R 13 ; —SO 2 NR 11 R 12 ; —C(R 13 ) z H (3-z) ; —CH 2 ) k R 14 ; and —(CH 2 ) k —Z—(CH 2 ) m —R 14 , where two or more R e groups may optionally be taken together to form an optionally substituted ring; and
R 10 at each occurrence can be independently selected from the group consisting of: hydrogen; —C(R 13 ) z H (3-z) ; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; up to a C 12 carbocycle; up to a C 12 heterocycle; —S(O) 2 R 13 ; —Si(R 15 ) 3 ; and a hydroxyl protecting group;
R 11 and R 12 at each occurrence can be independently selected from the group consisting of: hydrogen; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; and —C(R 13 ) z H (3-z) ;
R 11 and R 12 ; when both present, can optionally be taken together with the atom to which they are attached to form an optionally substituted 3- to 10-membered ring, optionally containing one or more additional heteroatoms;
R 13 at each occurrence can be independently selected from the group consisting of: hydrogen; halogen; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; up to a C 12 carbocycle; or up to a C 12 heterocycle;
R 14 at each occurrence can be independently selected from the group consisting of halogen; —OR 10 ; —OC(O)R 13 ; —OC(O)OR 13 ; —OC(O)NR 11 R 12 ; —CN; —CNO; —C(R 13 ) z H (3-z) ; —C(O)R 13 ; —C(O)OR 13 ; —C(O)NR 11 R 12 ; —NR 11 C(O)R 13 ; —NR 11 C(O)OR 10 ; —NR 11 SO 2 R 13 ; —NCO; —N 3 ; —NO 2 ; —S(O) x R 13 ; —SO 2 NR 11 R 12 ; up to a C 12 heterocycle; and up to a C 12 carbocycle;
R 15 at each occurrence can be independently selected from the group consisting of: C 1 to C 6 alkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; and up to C 12 substituted or unsubstituted carbocycle;
Z is a divalent linker and can be selected from the group consisting of: —(CH═CH) a —; —(CH≡CH) a —; —C(O)—; —C(═NOR 11 )—; —C(═NNR 11 R 12 )—; —O—; —N(R 11 )—; —N(C(O)R 13 )—; —S(O) x —; a polyether; and a polyamine;
a can be 1, 2, 3, or 4;
k can be an integer from 1 to 8 inclusive;
m can be an integer from 1 to 8 inclusive;
x can be 0, 1, or 2; and
z can be 1, 2, or 3; or

wherein the

moiety of S-Ia′ is selected from:

wherein R e at each occurrence is independently selected from the group consisting of: hydrogen; C 1 -C 12 alkyl; C 2 -C 12 alkenyl; C 2 -C 12 alkynyl; aryl; heteroaryl; halogen; —OR 10 ; —OC(O)R 13 ; —OC(O)OR 13 ; —OC(O)NR 11 R 12 ; —CN; —CNO; —C(O)R 13 ; —C(R 13 ) z H (3-z) ; —C(O)OR 13 ; —C(O)NR 11 R 12 ; —NR 11 R 12 ; —NR 11 C(O)R 10 ; —NR 11 C(O)OR 13 ; —NR 11 SO 2 R 13 ; —NCO; —N 3 ; —NO 2 ; —S(O) x R 13 , —SO 2 NR 11 R 12 ; —C(R 13 ) z H (3-z) ; —(CH 2 ) k R 14 ; and —(CH 2 ) k —Z—(CH 2 ) m —R 14 , where two or more R e groups may optionally be taken together to form an optionally substituted ring; and
R 10 at each occurrence can be independently selected from the group consisting of: hydrogen; —C(R 13 ) z H (3-z) ; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; up to a C 12 carbocycle; up to a C 12 heterocycle; —S(O) 2 R 13 ; —Si(R 15 ) 3 ; and a hydroxyl protecting group;
R 11 and R 12 at each occurrence can be independently selected from the group consisting of: hydrogen; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; and —C(R 13 ) z H (3-z) ;
R 11 and R 12 ; when both present, can optionally be taken together with the atom to which they are attached to form an optionally substituted 3- to 10-membered ring, optionally containing one or more additional heteroatoms;
R 13 at each occurrence can be independently selected from the group consisting of: hydrogen; halogen; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; up to a C 12 carbocycle; or up to a C 12 heterocycle;
R 14 at each occurrence can be independently selected from the group consisting of halogen; —OR 10 ; —OC(O)R 13 ; —OC(O)OR 13 ; —OC(O)NR 11 R 12 ; —CN; —CNO; —C(R 13 ) z H (3-z) ; —C(O)R 13 ; —C(O)OR 13 ; —C(O)NR 11 R 12 ; —NR 11 C(O)R 13 ; —NR 11 C(O)OR 10 ; —NR 11 SO 2 R 13 ; —NCO; —N 3 ; —NO 2 ; —S(O) x R 13 ; —SO 2 NR 11 R 12 ; up to a C 12 heterocycle; and up to a C 12 carbocycle;
R 15 at each occurrence can be independently selected from the group consisting of: C 1 to C 6 alkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; and up to C 12 substituted or unsubstituted carbocycle;
Z is a divalent linker and can be selected from the group consisting of: —(CH═CH) a —; —(CH≡CH) a —; —C(O)—; —C(═NOR 11 )—; —C(═NNR 11 R 12 )—; —O—; —N(R 11 )—; —N(C(O)R 13 )—; —S(O) x —; a polyether; and a polyamine;
a can be 1, 2, 3, or 4;
k can be an integer from 1 to 8 inclusive;
m can be an integer from 1 to 8 inclusive;
x can be 0, 1, or 2; and
z can be 1, 2, or 3; or

wherein the

moiety of S-Ia′ is selected from:

wherein:
R 10 at each occurrence can be independently selected from the group consisting of: hydrogen; —C(R 13 ) z H (3-z) ; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; up to a C 12 carbocycle; up to a C 12 heterocycle; —S(O) 2 R 13 ; —Si(R 15 ) 3 ; and a hydroxyl protecting group;
R 13 at each occurrence can be independently selected from the group consisting of: hydrogen; halogen; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; up to a C 12 carbocycle; or up to a C 12 heterocycle;
R 15 at each occurrence can be independently selected from the group consisting of: C 1 to C 6 alkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; and up to C 12 substituted or unsubstituted carbocycle; and
z can be 1, 2, or 3; or

wherein the

moiety of S-Ia′ is selected from:

wherein R e at each occurrence is independently selected from the group consisting of: hydrogen; C 1 -C 12 alkyl; C 2 -C 12 alkenyl; C 2 -C 12 alkynyl; aryl

Assignees

• Univ Cornell

Inventors

• Coates Geoffrey W
• Kramer John W

Classifications

• C07D309/30 Primary

  Oxygen atoms, e.g. delta-lactones · CPC title

• C07D405/06

  linked by a carbon chain containing only aliphatic carbon atoms · CPC title

• C07D311/96

  spiro-condensed with carbocyclic rings or ring systems · CPC title