Asymmetric allylation/Pauson-Khand reaction: a simple entry to polycyclic amines. Application to the synthesis of aminosteroid analogues
Fustero, Santos; Lázaro, Rubén; Aiguabella, Nuria; Riera, Antoni; Simón-Fuentes, Antonio; Barrio, Pablo; Organic Letters 16 (2014) 1224–1227; doi:10.1021/ol500142c

data_1513444
_publ_section_title
;
 Asymmetric allylation/Pauson-Khand reaction: a simple entry to polycyclic
 amines. Application to the synthesis of aminosteroid analogues
;
_journal_coden_ASTM              ORLEF7
_journal_issue                   4
_journal_name_full               'Organic Letters'
_journal_page_first              1224
_journal_page_last               1227
_journal_paper_doi               10.1021/ol500142c
_journal_volume                  16
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C24 H27 N O2 S, H2 O'
_chemical_formula_sum            'C24 H29 N O3 S'
_chemical_formula_weight         411.54
_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_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-12-11T15:27:50-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.86956(7)
_cell_length_b                   16.1458(2)
_cell_length_c                   22.8868(3)
_cell_measurement_reflns_used    10678
_cell_measurement_temperature    100.3(6)
_cell_measurement_theta_max      74.104
_cell_measurement_theta_min      3.323
_cell_measurement_wavelength     1.54184
_cell_volume                     2168.95(5)
_computing_cell_refinement       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_collection       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_reduction        'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_molecular_graphics    'Diamond v.3.2f (Crystal Impact GbR, 2008)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'OLEX2 (Dolomanov et al, 2010)'
_diffrn_ambient_temperature      100.3(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4023
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -64.00   35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.7631   38.0000  -90.0000 99

  2 omega  -68.00   -9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.7631   57.0000   30.0000 59

  3 omega  -64.00  -11.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   29.0000 -117.0000 53

  4 omega   29.00  108.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000   60.0000 79

  5 omega   35.00   62.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000   90.0000 27

  6 omega   37.00   73.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  150.0000 36

  7 omega   34.00   62.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -180.0000 28

  8 omega   34.00   59.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000   60.0000 25

  9 omega   65.00  109.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000   60.0000 44

 10 omega   27.00  140.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609    0.0000   60.0000 113

 11 omega   34.00   67.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  -60.0000 33

 12 omega    5.00   49.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.7631 -125.0000   90.0000 44

 13 omega   15.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.7631   57.0000  120.0000 91

 14 omega   59.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.7631 -125.0000   90.0000 39

 15 omega -152.00 -127.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000 -125.0000   30.0000 25

 16 omega  -51.00  -25.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   30.0000    0.0000 26

 17 omega   38.00   64.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000   30.0000 26

 18 omega   30.00   57.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -150.0000 27

 19 omega   31.00   83.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000  120.0000 52

 20 omega   34.00   99.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000    0.0000 65

 21 omega   52.00  142.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   15.0000  120.0000 90

 22 omega   35.00  110.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000  -30.0000 75

 23 omega   40.00  120.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000 -150.0000 80

 24 omega   74.00  113.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -61.0000  150.0000 39

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.091665
_diffrn_orient_matrix_UB_12      0.0522199
_diffrn_orient_matrix_UB_13      -0.0512096
_diffrn_orient_matrix_UB_21      -0.0319692
_diffrn_orient_matrix_UB_22      0.0793343
_diffrn_orient_matrix_UB_23      0.0365003
_diffrn_orient_matrix_UB_31      0.2438358
_diffrn_orient_matrix_UB_32      -0.0091603
_diffrn_orient_matrix_UB_33      0.0240105
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'Nova (Cu) X-ray micro-source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0241
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            16532
_diffrn_reflns_theta_full        70.99
_diffrn_reflns_theta_max         70.99
_diffrn_reflns_theta_min         3.35
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.518
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.80928
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
        (compiled Feb  1 2013,16:14:44)
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.26
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.4081
_exptl_crystal_size_mid          0.1348
_exptl_crystal_size_min          0.0885
_refine_diff_density_max         0.226
_refine_diff_density_min         -0.205
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (100%).
Analysis of the absolute structure using likelihood methods
(Hooft, Straver & Spek, 2008) was performed using PLATON (Spek, 2011).
 The results indicated that the absolute structure had been correctly
 assigned. The method calculated that the probability that the structure 
is inverted is smaller than 10-99. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=-0.017(6), which together with Flack parameter 
value, indicate that the absolute structure has sureley been determined 
correctly.

Flack, H. D. (1983), Acta Cryst. A39, 876-881
Flack & G. Bernardinelli, Acta Cryst. 1999, A55, 908-915; 
H. D. Flack & G. Bernardinelli, J. Appl. Cryst. 2000, 33, 1143-1148.

R. W. W. Hooft, L. H. Straver & A. L. Spek, J. Appl. Cryst. 2008, 41, 96-103
A. L. Spek (2010) PLATON, Utrecht, The Netherlands; 
A. L. Spek, J. Appl. Cryst. 2003, 36, 7-13
A. L. Thompson & D. J. Watkin, Tetrahedron: Asymmetry 2009, 20, 712--717

;
_refine_ls_abs_structure_Flack   0.016(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     278
_refine_ls_number_reflns         4172
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0261
_refine_ls_R_factor_gt           0.0254
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0385P)^2^+0.4289P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.066
_refine_ls_wR_factor_ref         0.0666
_reflns_number_gt                4083
_reflns_number_total             4172
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol500142c_si_002.cif
_cod_data_source_block           a2013132_bl763
_cod_depositor_comments
;
 Updated bibliographic information.

 Antanas Vaitkus,
 2019-09-22
;
_cod_original_cell_volume        2168.95(4)
_cod_database_code               1513444