A global and local desymmetrization approach to the synthesis of steroidal alkaloids: stereocontrolled total synthesis of paspaline.
Sharpe, Robert J.; Johnson, Jeffrey S.; Journal of the American Chemical Society 137 (2015) 4968–4971; doi:10.1021/jacs.5b02631

data_4129423
_publ_section_title
;
 A global and local desymmetrization approach to the synthesis of
 steroidal alkaloids: stereocontrolled total synthesis of paspaline.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4968
_journal_page_last               4971
_journal_paper_doi               10.1021/jacs.5b02631
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H39 N O2'
_chemical_formula_sum            'C28 H39 N O2'
_chemical_formula_weight         421.60
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-02-27
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.6682(4)
_cell_length_b                   18.2369(7)
_cell_length_c                   24.0876(10)
_cell_measurement_reflns_used    9820
_cell_measurement_temperature    100
_cell_measurement_theta_max      74.37
_cell_measurement_theta_min      3.04
_cell_volume                     4686.4(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0169
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            70995
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.468
_diffrn_reflns_theta_min         3.039
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.567
_exptl_absorpt_correction_T_max  0.9491
_exptl_absorpt_correction_T_min  0.8813
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0610 before and 0.0447 after correction.
The Ratio of minimum to maximum transmission is 0.9286.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_description       block
_exptl_crystal_F_000             1840
_exptl_crystal_size_max          0.298
_exptl_crystal_size_mid          0.191
_exptl_crystal_size_min          0.153
_refine_diff_density_max         0.392
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 3860 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     585
_refine_ls_number_reflns         9421
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0402
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0645P)^2^+0.9028P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1028
_refine_ls_wR_factor_ref         0.1044
_reflns_Friedel_coverage         0.797
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                9005
_reflns_number_total             9421
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b02631_si_001.cif
_cod_data_source_block           x1502014
_cod_database_code               4129423
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.849
_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:
 C11(H11), C12(H12), C16(H16), C19(H19), C39(H39), C40(H40), C44(H44), C47(H47)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C13(H13A,H13B), C14(H14A,H14B), C17(H17A,H17B),
 C18(H18A,H18B), C20(H20A,H20B), C37(H37A,H37B), C38(H38A,H38B), C41(H41A,H41B),
  C42(H42A,H42B), C45(H45A,H45B), C46(H46A,H46B), C48(H48A,H48B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2A), C3(H3), C4(H4), C29(H29), C30(H30), C31(H31), C32(H32)
2.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,
 H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              55961
_shelx_hkl_checksum              67618
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-02-23
_olex2_date_sample_submission    2015-02-23
_olex2_submission_original_sample_id RJS-1
_olex2_submission_special_instructions 'No special instructions were received'