Regioselective Spirostan E-Ring Opening for the Synthesis of Dihydropyran Steroidal Frameworks.
Hilario-Martínez, J Ciciolil; Zeferino-Díaz, Reyna; Muñoz-Hernández, Miguel A; Hernández-Linares, Ma Guadalupe; Cabellos, José Luis; Merino, Gabriel; Sandoval-Ramírez, Jesús; Jin, Zhendong; Fernández-Herrera, María A; Organic letters 18 (2016) 1772–1775; doi:10.1021/acs.orglett.6b00492

data_1542949
_publ_section_title
;
 Regioselective Spirostan E-Ring Opening for the Synthesis of Dihydropyran
 Steroidal Frameworks.
;
_journal_issue                   8
_journal_name_full               'Organic letters'
_journal_page_first              1772
_journal_page_last               1775
_journal_paper_doi               10.1021/acs.orglett.6b00492
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C29 H44 O4'
_chemical_formula_sum            'C29 H44 O4'
_chemical_formula_weight         456.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-02-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.5835(12)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.38314(17)
_cell_length_b                   6.24052(6)
_cell_length_c                   16.58575(16)
_cell_measurement_reflns_used    13303
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.2600
_cell_measurement_theta_min      5.5540
_cell_volume                     1334.28(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0769
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
  1 omega  -24.00   38.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059  -57.0000   30.0000 62

  2 omega   36.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059  -99.0000  120.0000 30

  3 omega   28.00   54.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059 -125.0000   30.0000 26

  4 omega   57.00   87.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059 -125.0000   30.0000 30

  5 omega   24.00   84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059 -125.0000  -90.0000 60

  6 omega   67.00  134.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -60.0000 67

  7 omega   83.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   60.0000 32

  8 omega   42.00  134.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000   90.0000 92

  9 omega   70.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000    0.0000 32

 10 omega   88.00  120.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   30.0000 32

 11 omega  118.00  173.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   30.0000 55

 12 omega  153.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   90.0000 25

 13 omega  152.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  150.0000 26

 14 omega  135.00  161.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 26

 15 omega  127.00  154.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 27

 16 omega  122.00  166.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 44

 17 omega  131.00  170.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 39

 18 omega  129.00  173.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 44

 19 omega  124.00  175.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 51

 20 omega  115.00  166.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 51

 21 omega  113.00  176.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 63

 22 omega   90.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 26

 23 omega   91.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  120.0000 25

 24 omega   88.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   90.0000 28

 25 omega   90.00  117.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   60.0000 27

 26 omega   90.00  117.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   30.0000 27

 27 omega   90.00  117.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -30.0000 27

 28 omega   90.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -60.0000 26

 29 omega   88.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -60.0000 30

 30 omega   87.00  119.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000    0.0000 32

 31 omega   87.00  155.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   60.0000 68

 32 omega   82.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 25

 33 omega   81.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 26

 34 omega   82.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 25

 35 omega  125.00  172.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 47

 36 omega  113.00  168.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 55

 37 omega   88.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -180.0000 27

 38 omega   88.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -150.0000 27

 39 omega   81.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 26

 40 omega   81.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 27

 41 omega   84.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   72.0000 -156.3014 26

 42 omega   88.00  131.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -90.0000 43

 43 omega   81.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 26

 44 omega   81.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 26

 45 omega   81.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 26

 46 omega   82.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 25

 47 omega   81.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 26

 48 omega   81.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 26

 49 omega   82.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 25

 50 omega   87.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  150.0000 26

 51 omega   87.00  117.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  120.0000 30

 52 omega   59.00   86.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   77.0000   90.0000 27

 53 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   38.0000   90.0000 84

 54 omega   25.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   77.0000  -60.0000 28

 55 omega   61.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   77.0000  -60.0000 42

 56 omega   71.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   19.0000 -150.0000 35

 57 omega   48.00   81.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   77.0000  -90.0000 33

 58 omega   30.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   38.0000 -120.0000 30

 59 omega   22.00   48.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   19.0000 -150.0000 26

 60 omega   13.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   77.0000 -150.0000 90

 61 omega   12.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   77.0000  -90.0000 33

 62 omega    2.00   29.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   91.0000  -11.5139 27

 63 omega   19.00   85.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   57.0000   30.0000 66

 64 omega   19.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   57.0000  120.0000 26

 65 omega   11.00   38.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   77.0000   90.0000 27

 66 omega  -31.00   55.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059  -77.0000  -60.0000 86

 67 omega   38.00  111.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -90.0000 73

 68 omega   44.00  101.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000 -120.0000 57

 69 omega   38.00   64.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   60.0000 26

 70 omega  -30.00   36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059  -57.0000   90.0000 66

 71 omega  -33.00   54.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059  -38.0000  150.0000 87

 72 omega    9.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   77.0000  150.0000 95

 73 omega    0.00   25.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2059   94.0000  -63.0992 25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0573761000
_diffrn_orient_matrix_UB_12      -0.1993747000
_diffrn_orient_matrix_UB_13      -0.0442896000
_diffrn_orient_matrix_UB_21      -0.0076761000
_diffrn_orient_matrix_UB_22      0.1041561000
_diffrn_orient_matrix_UB_23      -0.0856882000
_diffrn_orient_matrix_UB_31      0.1045131000
_diffrn_orient_matrix_UB_32      -0.1016912000
_diffrn_orient_matrix_UB_33      -0.0009623000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0208
_diffrn_reflns_av_unetI/netI     0.0155
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            18330
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.382
_diffrn_reflns_theta_min         4.953
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.577
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22403
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent colourless'
_exptl_crystal_density_diffrn    1.137
_exptl_crystal_description       prism
_exptl_crystal_F_000             500
_exptl_crystal_size_max          0.4500
_exptl_crystal_size_mid          0.2000
_exptl_crystal_size_min          0.0500
_refine_diff_density_max         0.415
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 2182 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     304
_refine_ls_number_reflns         5190
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0517
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0937P)^2^+0.2028P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1446
_refine_ls_wR_factor_ref         0.1455
_reflns_Friedel_coverage         0.803
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                5065
_reflns_number_total             5190
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b00492_si_001.cif
_cod_data_source_block           mm9
_cod_depositor_comments          'Adding full bibliography for 1542949.cif.'
_cod_database_code               1542949
_chemical_oxdiff_formula         C29H44O4
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1A), C7(H7), C8(H8), C14(H14), C15(H15), C16(H16), C18(H18), C23(H23)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C6(H6A,H6B), C9(H9A,H9B), C11(H11A,H11B), C12(H12A,
 H12B), C17(H17A,H17B), C21(H21A,H21B), C22(H22A,H22B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C20(H20)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              54425
_shelx_hkl_checksum              4977
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'