Table 7

Determination of the β-configuration of the 9,11-epoxide inD-3 and D-2 based on ¹H-NMR methyl chemical shifts data^7-a of 21-BMP, BOH, D-3,D-2, and reference steroids I–X shown in fig.2

Structure or structural change	Chemical shift [δ (ppm)] or shift difference		Reference
Structure or structural change	H-19	H-18	Reference
9α-Chloro,11β-hydroxy compounds
VIII	1.70	^7-b	Lack and Ridley, 1968
IX	1.70	1.18	Kaupp and Ulrich, 1992
X	1.67	^7-c	Kaupp and Ulrich, 1992
21-BMP	1.65	1.06	Table 5
BOH^7-d	1.62^7-d	0.98^7-d	Table 5
9β,11β-Epoxides
I	1.43	0.83	Holland and Riemland, 1985
II	1.45	1.11	Kaupp and Ulrich, 1992
III	1.43	0.79	Van Leusen and van Leusen, 1994
IV	1.43	0.83	Van Leusen and van Leusen, 1994
V	1.44	0.82	Annen et al., 1982
D-3	1.44	0.99	Table 5
D-2 ^7-d	1.37^7-d	0.86^7-d	Table5
9α,11α-Epoxides
VII	1.63	0.70	Holland and Riemland, 1985
VI(calculated)^7-e	1.44^7-e	0.66^7-e


9α-Cl,11β-OH → 9β,11β-epoxy
IX vs. II	−0.25	−0.07^7-f
VIII vs. I	−0.27	^7-b
X vs. I–V	−0.22 to−0.24	^c,f
21-BMP vs. D-3	−0.21	−0.07
BOH^7-d vs. D-2 ^7-d	−0.25	−0.12


9β,11β-Epoxy → 9α,11α-epoxy
I vs. VI	∼0	−0.17

↵7-a In CDCl₃ solvent unless otherwise stated.
↵7-b Not recorded.
↵7-c Not applicable.
↵7-d In CD₃SOCD₃ solvent.
↵7-e Methyl chemical shifts were not recorded (ApSimon et al., 1969). Data given have been calculated from those ofVII, taking into account the effect of 6β-OH (Bhacca and Williams, 1964; Kirk et al., 1990; Page, 1970;Zürcher, 1963).
↵7-f In comparison, the corresponding shift difference for 9α-Br,11β-OH → 9β,11β-epoxy is −0.07 and for 9α-F,11β-OH → 9β,11β-epoxy is −0.06, based on the data of epoxidesIII–V and their corresponding halohydrins (Annen et al., 1982; Van Leusen and van Leusen, 1994).