Catalyst-Directed Diastereoselective Isomerization of Allylic Alcohols for the Stereoselective Construction of C(20) in Steroid Side Chains: Scope and Topological Diversification.
Li, Houhua; Mazet, Clément; Journal of the American Chemical Society  (2015) 150811163019004–; doi:10.1021/jacs.5b06281

data_4124413
_publ_section_title
;
 Catalyst-Directed Diastereoselective Isomerization of Allylic Alcohols
 for the Stereoselective Construction of C(20) in Steroid Side Chains:
 Scope and Topological Diversification.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              150811163019004
_journal_paper_doi               10.1021/jacs.5b06281
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C35 H41 N O6'
_chemical_formula_sum            'C35 H41 N O6'
_chemical_formula_weight         571.69
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-07-10
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.09180(16)
_cell_length_b                   11.48593(15)
_cell_length_c                   25.4903(4)
_cell_measurement_reflns_used    12848
_cell_measurement_temperature    180.05(10)
_cell_measurement_theta_max      74.4310
_cell_measurement_theta_min      3.4350
_cell_volume                     2954.68(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      180.05(10)
_diffrn_detector_area_resol_mean 10.4679
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega  -67.00   33.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5000   77.0000  -90.0000 100

  2 omega  -49.00  -15.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5000   37.0000 -180.0000 34

  3 omega    1.00   34.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       41.7375  -99.0000 -180.0000 33

  4 omega   44.00   72.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -45.0000 -120.0000 28

  5 omega   40.00   66.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -30.0000  120.0000 26

  6 omega   63.00  100.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -94.0000  -90.0000 37

  7 omega   33.00   82.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -30.0000   30.0000 49

  8 omega   37.00   98.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -45.0000  -30.0000 61

  9 omega   87.00  174.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739   45.0000  150.0000 87

 10 omega   53.00   84.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       41.7375 -125.0000 -180.0000 31

 11 omega   46.00   88.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -45.0000  -90.0000 42

 12 omega   41.00   67.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -34.0000   71.0000 26

 13 omega  116.00  152.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -15.0000 -120.0000 36

 14 omega   51.00   77.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -94.0000  -47.0000 26

 15 omega   31.00   71.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -15.0000 -120.0000 40

 16 omega  -46.00   30.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5000   37.0000   60.0000 76

 17 omega  -17.00   23.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5000   37.0000 -180.0000 40

 18 omega    6.00   32.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       41.7375   19.0000   60.0000 26

 19 omega   31.00   64.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       41.7375  -99.0000   60.0000 33

 20 omega   76.00  120.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       41.7375   19.0000   60.0000 44

 21 omega   72.00  108.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -94.0000   30.0000 36

 22 omega   68.00  106.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -94.0000  -30.0000 38

 23 omega  141.00  175.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  125.0000 -150.0000 34

 24 omega  142.00  174.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739   45.0000   60.0000 32

 25 omega   55.00   84.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -94.0000 -120.0000 29

 26 omega   98.00  134.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739   45.0000   60.0000 36

 27 omega   45.00   84.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -45.0000  150.0000 39

 28 omega   36.00   89.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -30.0000 -180.0000 53

 29 omega   73.00  118.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739  -61.0000   60.0000 45

 30 omega   74.00  118.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0739 -125.0000 -150.0000 44
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1410410000
_diffrn_orient_matrix_UB_12      -0.0511287000
_diffrn_orient_matrix_UB_13      0.0018780000
_diffrn_orient_matrix_UB_21      -0.0187385000
_diffrn_orient_matrix_UB_22      0.0294546000
_diffrn_orient_matrix_UB_23      -0.0584764000
_diffrn_orient_matrix_UB_31      0.0552794000
_diffrn_orient_matrix_UB_32      -0.1204918000
_diffrn_orient_matrix_UB_33      -0.0151062000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0226
_diffrn_reflns_av_unetI/netI     0.0171
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            23362
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.680
_diffrn_reflns_theta_max         74.651
_diffrn_reflns_theta_min         3.468
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.700
_exptl_absorpt_correction_T_max  0.947
_exptl_absorpt_correction_T_min  0.859
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.285
_exptl_crystal_description       block
_exptl_crystal_F_000             1224
_exptl_crystal_size_max          0.2845
_exptl_crystal_size_mid          0.2696
_exptl_crystal_size_min          0.0804
_refine_diff_density_max         0.181
_refine_diff_density_min         -0.141
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
In the absence of significant anomalous scattering and no proper traitment of 
the data the absolute configuration is only indicative.
Flack parameter based on 2413 selcted parsons'quotients is 0.047(59)
Hooft is 0.03(5)

;
_refine_ls_abs_structure_Flack   0.05(18)
_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     382
_refine_ls_number_reflns         5993
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0303
_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^)+(0.0459P)^2^+0.3446P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0796
_refine_ls_wR_factor_ref         0.0816
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                5717
_reflns_number_total             5993
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b06281_si_003.cif
_cod_data_source_block           27
_cod_original_cell_volume        2954.67(7)
_cod_database_code               4124413
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 99.93
_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
2.a Ternary CH refined with riding coordinates:
 C14(H14), C20(H20), C28(H28), C11(H11), C19(H19), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C21(H21A,H21B), C27(H27A,H27B), C26(H26A,H26B), C17(H17A,
 H17B), C18(H18A,H18B), C13(H13A,H13B), C3(H3A,H3B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C39(H39), C36(H36), C9(H9), C7(H7), C8(H8), C6(H6), C38(H38),
 C10(H10), C35(H35), C2(H2)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C25(H25A,H25B,H25C)
;
_olex2_submission_special_instructions 'No special instructions were received'