Allenylic Carbonates in Enantioselective Iridium-Catalyzed Alkylations.
Petrone, David A.; Isomura, Mayuko; Franzoni, Ivan; Rössler, Simon L; Carreira, Erick M.; Journal of the American Chemical Society 140 (2018) 4697–4704; doi:10.1021/jacs.8b01416

data_4132079
_publ_section_title
;
 Allenylic Carbonates in Enantioselective Iridium-Catalyzed Alkylations.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4697
_journal_page_last               4704
_journal_paper_doi               10.1021/jacs.8b01416
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H24 Br N O2'
_chemical_formula_sum            'C25 H24 Br N O2'
_chemical_formula_weight         450.36
_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             2017-10-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.16730(10)
_cell_length_b                   8.87340(10)
_cell_length_c                   46.1987(4)
_cell_measurement_reflns_used    60981
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.2260
_cell_measurement_theta_min      3.8040
_cell_volume                     2118.28(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.23a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.23a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.23a (Rigaku OD, 2015)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 0.999
_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     -7.00  23.00   0.50    0.10    --   26.00  97.00-146.82   60
  2  \w     34.00 121.00   0.50    0.10    --   49.37  57.00 -90.00  174
  3  \w     69.00 157.00   0.50    0.50    --   86.00  61.00 -98.54  176
  4  \w    136.00 163.00   0.50    0.50    --  110.00  77.00 -60.00   54
  5  \w    129.00 177.00   0.50    0.50    --  110.00  77.00 -90.00   96
  6  \w    134.00 160.00   0.50    0.50    --  110.00  77.00-180.00   52
  7  \w     94.00 178.00   0.50    0.50    --  110.00  57.00-120.00  168
  8  \w    103.00 128.00   0.50    0.50    --  110.00  38.00   0.00   50
  9  \w     87.00 168.00   0.50    0.50    --  110.00  77.00   0.00  162
 10  \w    129.00 164.00   0.50    0.50    --  102.00  78.00 154.90   70
 11  \w    138.00 176.00   0.50    0.50    --  110.00  77.00 150.00   76
 12  \w     96.00 176.00   0.50    0.50    --  110.00  57.00  90.00  160
 13  \w     94.00 178.00   0.50    0.50    --  110.00  57.00  60.00  168
 14  \w     97.00 129.00   0.50    0.50    --  110.00  77.00 150.00   64
 15  \w     86.00 171.00   0.50    0.50    --  110.00  77.00 120.00  170
 16  \w     94.00 131.00   0.50    0.50    --  110.00  57.00  30.00   74
 17  \w     87.00 171.00   0.50    0.50    --  110.00  77.00 -30.00  168
 18  \w     94.00 174.00   0.50    0.50    --  110.00  57.00-150.00  160
 19  \w     96.00 152.00   0.50    0.50    --  110.00  57.00 -60.00  112
 20  \w     86.00 118.00   0.50    0.50    --  110.00  77.00 -60.00   64
 21  \w     74.00 162.00   0.50    0.50    --   90.00  58.00 -82.28  176
 22  \w     86.00 124.00   0.50    0.50    --  110.00  77.00 -90.00   76
 23  \w     86.00 116.00   0.50    0.50    --  110.00  77.00-180.00   60
 24  \w     57.00 146.00   0.50    0.10    --   78.00  70.00-145.62  178
 25  \w     58.00 146.00   0.50    0.10    --   78.00  69.00-161.93  176
 26  \w     86.00 169.00   0.50    0.50    --  110.00  77.00  30.00  166
 27  \w     75.00 162.00   0.50    0.50    --   90.00  55.00  98.80  174
 28  \w     79.00 105.00   0.50    0.50    --  102.00  78.00 154.90   52
 29  \w     77.00 165.00   0.50    0.50    --   94.00  61.00 110.26  176
 30  \w     61.00 149.00   0.50    0.10    --   78.00  61.00 154.12  176
 31  \w     56.00 144.00   0.50    0.10    --   74.00  63.00  84.08  176
 32  \w     37.00 125.00   0.50    0.10    --   49.37  38.00 120.00  176
 33  \w     60.00 130.00   0.50    0.50    --  110.00 -77.00 -30.00  140
 34  \w     86.00 122.00   0.50    0.50    --  110.00-125.00 -30.00   72
 35  \w     73.00 102.00   0.50    0.50    --  110.00 -99.00 -30.00   58
 36  \w     53.00  79.00   0.50    0.50    --  110.00-125.00 -30.00   52
 37  \w     44.00  69.00   0.50    0.50    --  110.00 -99.00 -30.00   50
 38  \w     38.00  84.00   0.50    0.50    --  110.00 -57.00  60.00   92
 39  \w     66.00  95.00   0.50    0.50    --  110.00 -99.00 150.00   58
 40  \w     96.00 122.00   0.50    0.50    --  110.00-125.00  90.00   52
 41  \w     41.00  76.00   0.50    0.50    --  110.00-125.00  90.00   70
 42  \w     27.00  95.00   0.50    0.10    --   49.37-120.00  58.00  136
 43  \w     42.00 102.00   0.50    0.50    --  110.00 -99.00-150.00  120
 44  \w     48.00  74.00   0.50    0.50    --  110.00 -57.00-150.00   52
 45  \w     43.00  79.00   0.50    0.50    --  110.00 -57.00-180.00   72
 46  \w     36.00 125.00   0.50    0.10    --   58.00  73.00  -8.37  178
 47  \w     37.00 125.00   0.50    0.10    --   49.37  38.00  30.00  176
 48  \w     33.00 121.00   0.50    0.10    --   54.00  72.00  55.76  176
 49  \w     33.00 121.00   0.50    0.10    --   54.00  72.00 134.76  176
 50  \w     32.00 121.00   0.50    0.10    --   54.00  73.00 165.70  178
 51  \w      4.00  30.00   0.50    0.10    --   34.00  90.00 -41.25   52
 52  \w     -7.00  24.00   0.50    0.10    --   26.00  96.00 167.71   62
 53  \w   -125.00 -37.00   0.50    0.10    --  -49.37 -19.00  90.00  176
 54  \w   -125.00 -37.00   0.50    0.10    --  -49.37 -19.00 -90.00  176
 55  \w    -94.00  -3.00   0.50    0.50    --  -70.00  77.00-180.00  182
 56  \w   -125.00 -36.00   0.50    0.10    --  -58.00 -73.00  39.51  178
 57  \w   -120.00 -38.00   0.50    0.10    --  -49.37-178.00 120.00  164
 58  \w   -125.00 -36.00   0.50    0.10    --  -58.00 -73.00 129.88  178
 59  \w   -129.00 -41.00   0.50    0.50    --  -62.00 -71.00 -33.24  176
 60  \w   -133.00 -44.00   0.50    0.50    --  -66.00 -73.00-134.61  178
 61  \w   -137.00 -48.00   0.50    0.50    --  -70.00 -73.00 -41.10  178
 62  \w   -137.00 -48.00   0.50    0.50    --  -70.00 -72.00-103.14  178
 63  \w   -137.00 -48.00   0.50    0.50    --  -70.00 -73.00  43.66  178
 64  \w   -137.00 -48.00   0.50    0.50    --  -70.00 -73.00 172.80  178
 65  \w   -138.00 -50.00   0.50    0.50    --  -70.00 -68.00 134.89  176
 66  \w   -139.00 -51.00   0.50    0.50    --  -70.00 -66.00 -37.97  176
 67  \w   -138.00 -49.00   0.50    0.50    --  -70.00 -69.00 -69.72  178
 68  \w   -139.00 -51.00   0.50    0.50    --  -70.00 -66.00 -15.78  176
 69  \w   -138.00 -50.00   0.50    0.50    --  -70.00 -68.00  75.46  176
 70  \w   -138.00 -49.00   0.50    0.50    --  -70.00 -69.00 117.34  178
 71  \w   -139.00 -51.00   0.50    0.50    --  -70.00 -65.00  87.30  176
 72  \w   -139.00 -51.00   0.50    0.50    --  -70.00 -65.00   7.56  176
 73  \w   -137.00 -48.00   0.50    0.50    --  -70.00 -73.00-154.75  178
;
_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      -0.0178503000
_diffrn_orient_matrix_UB_12      -0.1703143000
_diffrn_orient_matrix_UB_13      -0.0061684000
_diffrn_orient_matrix_UB_21      -0.0382701000
_diffrn_orient_matrix_UB_22      -0.0305176000
_diffrn_orient_matrix_UB_23      0.0325375000
_diffrn_orient_matrix_UB_31      -0.2951546000
_diffrn_orient_matrix_UB_32      0.0142886000
_diffrn_orient_matrix_UB_33      -0.0038854000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0561
_diffrn_reflns_av_unetI/netI     0.0181
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       58
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            78643
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.755
_diffrn_reflns_theta_min         3.827
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.803
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.692
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.23a (Rigaku Oxford Diffraction, 2015)
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    1.412
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.153
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.043
_refine_diff_density_max         0.874
_refine_diff_density_min         -0.994
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details
;
 Flack x determined using 1750 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.011(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.221
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     317
_refine_ls_number_reflns         4569
_refine_ls_number_restraints     173
_refine_ls_restrained_S_all      1.206
_refine_ls_R_factor_all          0.0519
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0169P)^2^+8.8441P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1290
_refine_ls_wR_factor_ref         0.1293
_reflns_Friedel_coverage         0.676
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                4516
_reflns_number_total             4569
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b01416_si_003.cif
_cod_data_source_block           ca280917_1_1
_cod_database_code               4132079
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C25H24BrNO2
_reflns_odcompleteness_completeness 99.87
_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, All N(H) groups
2. Restrained distances
 N1-H1
 0.93 with sigma of 0.02
 C25-H25A = C25-H25B
 0.86 with sigma of 0.001
 H25A-H25B
 1.49 with sigma of 0.001
 N1-C3A \\sim N1-C3
 with sigma of 0.02
 N1-C6A \\sim N1-C4A
 with sigma of 0.02
 Br1-C5 \\sim Br1A-C5A
 with sigma of 0.02
 Br1A-C1A \\sim Br1A-C10A
 with sigma of 0.02
3. Restrained planarity
 C22, C25, H25A, H25B
 with sigma of 0.001
 N1, C3A, C6A, C10A, C5A, C1A, C4A, Br1A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C3A) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C5A)
\\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C4A) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(Br1) = Uanis(Br1A)
5. Rigid body (RIGU) restrains
 C17, C18, C22, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C3, C4, C5, C6, C1A, C3A, C4A, C5A, C6A, C10, C10A, Br1, Br1A, N1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C3A)=Sof(C6A)=Sof(H6A)=Sof(C10A)=Sof(H10A)=Sof(C5A)=Sof(C1A)=Sof(H1AA)=
 Sof(C4A)=Sof(H4A)=Sof(Br1A)=1-FVAR(1)
 Sof(Br1)=Sof(C1)=Sof(H1A)=Sof(C3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(C6)=Sof(H6)=
 Sof(C10)=Sof(H10)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C17(H17)
7.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C13(H13A,H13B), C23(H23A,H23B)
7.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C4(H4), C6(H6), C9(H9), C10(H10), C12(H12), C15(H15), C16(H16),
 C18(H18), C20(H20), C21(H21), C24(H24), C6A(H6A), C10A(H10A), C1A(H1AA),
 C4A(H4A)
7.d Fitted hexagon refined as free rotating group:
 C3A(C6A,C10A,C5A,C1A,C4A)
;
_shelx_res_checksum              82245
_shelx_hkl_checksum              77099
_olex2_date_sample_data_collection 2017-10-28
_olex2_date_sample_submission    2017-10-28
_olex2_submission_original_sample_id ca280917_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 1.246
_oxdiff_exptl_absorpt_empirical_full_min 0.841