Total Synthesis of (-)-Mitrephorone A.
Richter, Matthieu J. R.; Schneider, Michael; Brandstätter, Marco; Krautwald, Simon; Carreira, Erick M.; Journal of the American Chemical Society 140 (2018) 16704–16710; doi:10.1021/jacs.8b09685

data_4133334
_publ_section_title
;
 Total Synthesis of (-)-Mitrephorone A.
;
_journal_issue                   48
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16704
_journal_page_last               16710
_journal_paper_doi               10.1021/jacs.8b09685
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H43 N O3 Si'
_chemical_formula_sum            'C26 H43 N O3 Si'
_chemical_formula_weight         445.70
_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     dual
_audit_creation_date             2018-09-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.75079(4)
_cell_length_b                   17.50986(9)
_cell_length_c                   18.79506(9)
_cell_measurement_reflns_used    53277
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      79.4420
_cell_measurement_theta_min      3.4280
_cell_volume                     2550.78(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -92.00 -12.00   0.50    0.11    --  -70.00 125.00 -60.00  160
  2  \w     17.00  42.00   0.50    0.10    --   46.00  88.00  12.69   50
  3  \w     52.00  89.00   0.50    0.10    --   78.00  83.00 -55.59   74
  4  \w     94.00 145.00   0.50    0.11    --  110.00  57.00-120.00  102
  5  \w     94.00 178.00   0.50    0.11    --  110.00  57.00-180.00  168
  6  \w     86.00 171.00   0.50    0.11    --  110.00  77.00   0.00  170
  7  \w     69.00  98.00   0.50    0.11    --   94.00  81.00  24.66   58
  8  \w    118.00 144.00   0.50    0.11    --   94.00  81.00  24.66   52
  9  \w     97.00 123.00   0.50    0.11    --  110.00  57.00 120.00   52
 10  \w    142.00 168.00   0.50    0.11    --  110.00  57.00 120.00   52
 11  \w     68.00  95.00   0.50    0.10    --   58.00  76.00  72.93   54
 12  \w     34.00  75.00   0.50    0.10    --   58.00  79.00 162.94   82
 13  \w     39.00  65.00   0.50    0.10    --   58.00  76.00  72.93   52
 14  \w     35.00  60.00   0.50    0.10    --   58.00  79.00  43.99   50
 15  \w    111.00 149.00   0.50    0.11    --   82.00  73.00 105.49   76
 16  \w     63.00 111.00   0.50    0.11    --   82.00  65.00 168.88   96
 17  \w     60.00  94.00   0.50    0.11    --   82.00  73.00 105.49   68
 18  \w     34.00  63.00   0.50    0.10    --   58.00  78.00 -63.90   58
 19  \w     35.00  64.00   0.50    0.10    --   58.00  76.00-115.22   58
 20  \w     54.00 120.00   0.50    0.10    --   78.00  79.00-143.75  132
 21  \w     66.00 109.00   0.50    0.11    --   86.00  69.00-112.45   86
 22  \w     88.00 119.00   0.50    0.11    --  110.00  77.00-180.00   62
 23  \w     97.00 178.00   0.50    0.11    --  110.00  57.00-150.00  162
 24  \w    114.00 154.00   0.50    0.11    --   86.00  69.00-112.45   80
 25  \w     99.00 124.00   0.50    0.11    --  110.00  38.00 -60.00   50
 26  \w     86.00 171.00   0.50    0.11    --  110.00  77.00 -30.00  170
 27  \w    127.00 166.00   0.50    0.11    --  110.00  77.00  90.00   78
 28  \w    140.00 177.00   0.50    0.11    --  110.00  77.00 150.00   74
 29  \w     86.00 125.00   0.50    0.11    --  110.00  77.00 150.00   78
 30  \w     87.00 112.00   0.50    0.11    --  110.00  77.00  90.00   50
 31  \w     87.00 116.00   0.50    0.11    --  110.00  77.00  30.00   58
 32  \w     95.00 178.00   0.50    0.11    --  110.00  57.00  60.00  166
 33  \w    143.00 175.00   0.50    0.11    --  110.00  77.00  30.00   64
 34  \w    101.00 155.00   0.50    0.11    --  110.00  38.00  90.00  108
 35  \w     94.00 154.00   0.50    0.11    --  110.00  57.00 -30.00  120
 36  \w     88.00 170.00   0.50    0.11    --  110.00  77.00 -60.00  164
 37  \w     88.00 115.00   0.50    0.11    --  110.00  77.00-120.00   54
 38  \w    146.00 174.00   0.50    0.11    --  110.00  77.00-120.00   56
 39  \w    119.00 174.00   0.50    0.11    --  110.00  77.00 -90.00  110
 40  \w     86.00 111.00   0.50    0.11    --  110.00  77.00 -90.00   50
 41  \w    139.00 174.00   0.50    0.11    --  110.00  77.00 120.00   70
 42  \w     90.00 130.00   0.50    0.11    --  110.00  77.00 120.00   80
 43  \w    -93.00  -5.00   0.50    0.11    --  -70.00  77.00-150.00  176
 44  \w   -122.00 -77.00   0.50    0.10    --  -49.37 -38.00-120.00   90
 45  \w     41.00  81.00   0.50    0.11    --  110.00 -57.00  30.00   80
 46  \w     52.00  79.00   0.50    0.11    --  110.00 -77.00 -30.00   54
 47  \w     88.00 121.00   0.50    0.11    --  110.00 -77.00 -30.00   66
 48  \w     44.00 134.00   0.50    0.11    --  110.00 -77.00 120.00  180
 49  \w    -67.00 -37.00   0.50    0.10    --  -49.37 -38.00-120.00   60
 50  \w   -124.00 -38.00   0.50    0.10    --  -49.37 -19.00  90.00  172
 51  \w    -66.00 -41.00   0.50    0.10    --  -49.37 -44.00  54.34   50
 52  \w   -116.00 -91.00   0.50    0.10    --  -49.37 -46.00 -39.38   50
 53  \w    -88.00 -38.00   0.50    0.10    --  -49.37 -46.00 -39.38  100
 54  \w     35.00  78.00   0.50    0.10    --   49.37  57.00-150.00   86
 55  \w     34.00  72.00   0.50    0.10    --   49.37  57.00  60.00   76
 56  \w     39.00  82.00   0.50    0.10    --   49.37  19.00  60.00   86
 57  \w     85.00 112.00   0.50    0.10    --   49.37  19.00  60.00   54
 58  \w     36.00  82.00   0.50    0.10    --   49.37  57.00 120.00   92
 59  \w     26.00  54.00   0.50    0.10    --   49.37  77.00 150.00   56
 60  \w     26.00  52.00   0.50    0.10    --   49.37  77.00 -60.00   52
 61  \w     35.00  60.00   0.50    0.10    --   49.37  57.00 -90.00   50
 62  \w     42.00  67.00   0.50    0.10    --   49.37  38.00-150.00   50
 63  \w     60.00 103.00   0.50    0.11    --  110.00 -99.00  30.00   86
 64  \w     40.00 106.00   0.50    0.11    --  110.00 -99.00 -30.00  132
 65  \w     44.00  98.00   0.50    0.11    --  110.00 -99.00 -60.00  108
 66  \w     67.00  93.00   0.50    0.11    --  110.00 -99.00-120.00   52
 67  \w     90.00 115.00   0.50    0.11    --  110.00-125.00 -90.00   50
 68  \w     51.00 120.00   0.50    0.11    --  110.00-125.00 150.00  138
 69  \w    -76.00 -46.00   0.50    0.11    --  -70.00 -77.00  90.00   60
 70  \w    -77.00 -51.00   0.50    0.11    --  -70.00 -70.00 148.93   52
 71  \w   -135.00 -97.00   0.50    0.11    --  -70.00 -77.00  90.00   76
 72  \w    -80.00 -46.00   0.50    0.11    --  -70.00 -77.00  60.00   68
 73  \w    -73.00 -46.00   0.50    0.11    --  -70.00 -77.00  30.00   54
 74  \w    -71.00 -45.00   0.50    0.11    --  -70.00 -79.00 -24.88   52
 75  \w    -72.00 -47.00   0.50    0.11    --  -70.00 -77.00-180.00   50
 76  \w    -75.00 -47.00   0.50    0.11    --  -70.00 -77.00 -90.00   56
 77  \w    -76.00 -44.00   0.50    0.11    --  -70.00 -82.00 -44.05   64
 78  \w   -120.00 -40.00   0.50    0.10    --  -49.37-178.00 -60.00  160
 79  \w    -69.00 -44.00   0.50    0.11    --  -70.00 -81.00-138.05   50
 80  \w    -69.00 -44.00   0.50    0.11    --  -70.00 -83.00-102.64   50
 81  \w    -70.00 -43.00   0.50    0.11    --  -70.00 -83.00   9.42   54
 82  \w    -71.00 -46.00   0.50    0.11    --  -70.00 -81.00 117.04   50
 83  \w    -69.00 -44.00   0.50    0.11    --  -70.00 -81.00 129.92   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1829364000
_diffrn_orient_matrix_UB_12      0.0343777000
_diffrn_orient_matrix_UB_13      0.0019359000
_diffrn_orient_matrix_UB_21      -0.0037609000
_diffrn_orient_matrix_UB_22      0.0014636000
_diffrn_orient_matrix_UB_23      -0.0819235000
_diffrn_orient_matrix_UB_31      -0.0777570000
_diffrn_orient_matrix_UB_32      -0.0809708000
_diffrn_orient_matrix_UB_33      -0.0007201000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0413
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            65578
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.797
_diffrn_reflns_theta_min         3.450
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.007
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.505
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.31d (Rigaku Oxford Diffraction, 2017) Numerical absorption correction based on gaussian integration over 			a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.161
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_recrystallization_method
'crystallized from a diethylether/hexane mixture'
_exptl_crystal_size_max          0.219
_exptl_crystal_size_mid          0.171
_exptl_crystal_size_min          0.156
_refine_diff_density_max         0.202
_refine_diff_density_min         -0.192
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 2293 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     294
_refine_ls_number_reflns         5499
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0274
_refine_ls_R_factor_gt           0.0271
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0416P)^2^+0.4845P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0707
_refine_ls_wR_factor_ref         0.0710
_reflns_Friedel_coverage         0.756
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                5427
_reflns_number_total             5499
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09685_si_002.cif
_cod_data_source_block           c230918_1_1
_cod_database_code               4133334
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C26H43NO3Si
_reflns_odcompleteness_completeness 99.92
_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. Restrained distances
 N1-H1B = N1-H1A
 0.93 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C3(H3), C8(H8), C12(H12)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B), C7(H7A,H7B), C10(H10A,H10B), C15(H15A,H15B),
 C16(H16A,H16B), C17(H17A,H17B), C21(H21A,H21B), C23(H23A,H23B), C25(H25A,H25B)
3.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C14(H14A,H14B,H14C), C20(H20A,H20B,H20C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              6618
_shelx_hkl_checksum              23396
_olex2_date_sample_submission    2018-09-24
_olex2_exptl_crystal_mounting_method tip-mounted
_olex2_submission_original_sample_id c230918_1_1
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
'Empirical correction (ABSPACK) includes: - Absorption correction using spherical harmonics - Frame scaling - Detector area scaling'
_oxdiff_exptl_absorpt_empirical_full_max 1.175
_oxdiff_exptl_absorpt_empirical_full_min 0.871