US 12,227,537 B2
Intermediates for the preparation of 11-methylene steroids
Celso Miguel Sandoval Rodríguez, Boecillo-Valladolid (ES); Ignacio Herráiz Sierra, Boecillo-Valladolid (ES); Ivano Messina, Boecillo-Valladolid (ES); and Jesús Miguel Iglesias Retuerto, Boecillo-Valladolid (ES)
Assigned to CRYSTAL PHARMA, S.A.U., Boecillo-Valladolid (ES)
Filed by CRYSTAL PHARMA, S.A.U., Boecillo-Valladolid (ES)
Filed on May 13, 2021, as Appl. No. 17/319,545.
Application 17/319,545 is a division of application No. 16/081,835, granted, now 11,034,716, previously published as PCT/EP2017/054952, filed on Mar. 2, 2017.
Claims priority of application No. 16382092 (EP), filed on Mar. 3, 2016.
Prior Publication US 2021/0269474 A1, Sep. 2, 2021
Int. Cl. C07J 11/00 (2006.01); C07J 1/00 (2006.01); C07J 21/00 (2006.01); C07J 33/00 (2006.01); C07J 43/00 (2006.01); C07J 51/00 (2006.01)
CPC C07J 11/00 (2013.01) [C07J 1/0059 (2013.01); C07J 1/0096 (2013.01); C07J 21/008 (2013.01); C07J 33/007 (2013.01); C07J 43/003 (2013.01); C07J 51/00 (2013.01); C07J 1/007 (2013.01); C07J 1/0077 (2013.01); C07J 1/0085 (2013.01)] 4 Claims
 
1. A compound of formula (Ic):

OG Complex Work Unit Chemistry
wherein:
X represents H or it forms together with the carbon atom to which it is bonded a ketone protecting group;
Z is selected from H and SiR′3 wherein each R′ is independently selected from C1-C6 alkyl and C6-C10 aryl;
R6 is selected from H, C1-C6 alkyl and halogen;
R10 is selected from H, C1-C6 alkyl and halogen, or is absent when there is a double bond between C1 and C10;
R13 is selected from H and C1-C6 alkyl;
R16 is selected from H, C1-C6 alkyl and halogen; and
custom character is a single or double bond;
said compound meeting one of the following conditions (a) to (c):
(a) wherein Z is SiR′3 wherein each R′ is independently selected from C1-C6 alkyl and C6-C10 aryl;
(b) with the proviso that the compound of formula (Ic) does not represent:

OG Complex Work Unit Chemistry
(c) which is selected from:
a compound of formula (Ia-1):

OG Complex Work Unit Chemistry
wherein:
X forms together with the carbon atom to which it is bonded a ketone protecting group;
Z is selected from H and SiR′3 wherein each R′ is independently selected from C1-C6 alkyl and C6-C10 aryl; and
custom character is a single or double bond;
and
a compound of formula (Ib-1):

OG Complex Work Unit Chemistry
wherein:
Z is selected from H and SiR′3 wherein each R′ is independently selected from C1-C6 alkyl and C6-C10 aryl.