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_4132078
_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_formula_moiety         'C83 H62 Cl Ir N2 O7 P2, 4(C H Cl3)'
_chemical_formula_sum            'C87 H66 Cl13 Ir N2 O7 P2'
_chemical_formula_weight         1966.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 117.361(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.2502(4)
_cell_length_b                   12.94850(10)
_cell_length_c                   28.5346(4)
_cell_measurement_reflns_used    59613
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.0750
_cell_measurement_theta_min      3.4950
_cell_volume                     9270.2(3)
_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    '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 1.000
_diffrn_measured_fraction_theta_max 0.985
_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    -63.00  26.00   0.50    0.78    --  -49.37  38.00 120.00  178
  2  \w     78.00 116.00   0.50    0.78    --   49.37  77.00 -60.00   76
  3  \w     91.00 178.00   0.50    3.12    --  110.00 125.00   0.00  174
  4  \w    153.00 178.00   0.50    3.12    --  110.00  57.00 120.00   50
  5  \w     98.00 178.00   0.50    3.12    --  110.00  38.00  60.00  160
  6  \w    100.00 148.00   0.50    3.12    --  110.00 125.00  60.00   96
  7  \w     94.00 147.00   0.50    3.12    --  110.00  57.00 120.00  106
  8  \w     96.00 123.00   0.50    3.12    --  110.00 -19.00  90.00   54
  9  \w     62.00  90.00   0.50    3.12    --  110.00 -99.00 150.00   56
 10  \w     50.00  78.00   0.50    3.12    --  110.00 -57.00  90.00   56
 11  \w     62.00 110.00   0.50    3.12    --  110.00 -99.00  60.00   96
 12  \w     69.00 120.00   0.50    3.12    --  110.00-125.00  60.00  102
 13  \w     38.00  84.00   0.50    3.12    --  110.00 -57.00 150.00   92
 14  \w     39.00 115.00   0.50    3.12    --  110.00-108.00 106.00  152
 15  \w     39.00 122.00   0.50    3.12    --  110.00-125.00 -30.00  166
 16  \w     44.00 104.00   0.50    3.12    --  110.00 -99.00-180.00  120
 17  \w     94.00 119.00   0.50    3.12    --  110.00 -19.00 -90.00   50
 18  \w     94.00 121.00   0.50    3.12    --  110.00 -19.00-120.00   54
 19  \w    101.00 171.00   0.50    3.12    --  110.00  19.00-180.00  140
 20  \w    128.00 161.00   0.50    3.12    --  110.00  77.00-120.00   66
 21  \w    106.00 146.00   0.50    3.12    --  110.00 108.00-157.00   80
 22  \w     89.00 116.00   0.50    3.12    --  110.00  77.00-120.00   54
 23  \w     94.00 119.00   0.50    3.12    --  110.00 -19.00-150.00   50
 24  \w     94.00 119.00   0.50    3.12    --  110.00 -19.00-180.00   50
 25  \w     38.00  84.00   0.50    3.12    --  110.00 -57.00 -60.00   92
 26  \w     40.00  94.00   0.50    3.12    --  110.00 -99.00 -30.00  108
 27  \w     38.00  63.00   0.50    3.12    --  110.00 -57.00-120.00   50
 28  \w     45.00  74.00   0.50    3.12    --  110.00 -57.00-150.00   58
 29  \w     39.00  76.00   0.50    3.12    --  110.00 -57.00-180.00   74
 30  \w     39.00  67.00   0.50    3.12    --  110.00 -57.00 -30.00   56
 31  \w     42.00  84.00   0.50    3.12    --  110.00 -57.00   0.00   84
 32  \w     38.00  81.00   0.50    3.12    --  110.00 -57.00  60.00   86
 33  \w     40.00  67.00   0.50    3.12    --  110.00-125.00  60.00   54
 34  \w   -116.00 -78.00   0.50    0.78    --  -49.37 -77.00-150.00   76
 35  \w     59.00 120.00   0.50    0.78    --   49.37 178.00-120.00  122
 36  \w     59.00 120.00   0.50    0.78    --   49.37 178.00-180.00  122
 37  \w    -83.00   6.00   0.50    3.12    --  -70.00  19.00 120.00  178
 38  \w    -95.00  -9.00   0.50    3.12    --  -70.00 125.00 -60.00  172
 39  \w   -116.00 -78.00   0.50    0.78    --  -49.37 -77.00-180.00   76
 40  \w   -137.00 -78.00   0.50    3.12    --  -70.00 -77.00 -30.00  118
 41  \w   -116.00 -78.00   0.50    0.78    --  -49.37 -77.00  30.00   76
 42  \w   -141.00 -75.00   0.50    3.12    --  -70.00-125.00 150.00  132
 43  \w   -120.00 -38.00   0.50    0.78    --  -49.37-178.00 120.00  164
 44  \w   -140.00 -84.00   0.50    3.12    --  -70.00 -99.00  60.00  112
 45  \w   -146.00 -57.00   0.50    3.12    --  -70.00 -19.00 120.00  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      -0.0056281000
_diffrn_orient_matrix_UB_12      0.0378819000
_diffrn_orient_matrix_UB_13      -0.0534943000
_diffrn_orient_matrix_UB_21      0.0604820000
_diffrn_orient_matrix_UB_22      0.0200695000
_diffrn_orient_matrix_UB_23      0.0254058000
_diffrn_orient_matrix_UB_31      0.0089179000
_diffrn_orient_matrix_UB_32      -0.1109671000
_diffrn_orient_matrix_UB_33      -0.0137518000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0767
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            144630
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.014
_diffrn_reflns_theta_min         3.101
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.974
_exptl_absorpt_correction_T_max  0.903
_exptl_absorpt_correction_T_min  0.353
_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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.409
_exptl_crystal_description       plate
_exptl_crystal_F_000             3944
_exptl_crystal_size_max          0.184
_exptl_crystal_size_mid          0.172
_exptl_crystal_size_min          0.033
_refine_diff_density_max         2.991
_refine_diff_density_min         -1.819
_refine_diff_density_rms         0.146
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.583
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1034
_refine_ls_number_reflns         19954
_refine_ls_number_restraints     166
_refine_ls_restrained_S_all      1.595
_refine_ls_R_factor_all          0.0808
_refine_ls_R_factor_gt           0.0739
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1230P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2376
_refine_ls_wR_factor_ref         0.2433
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17212
_reflns_number_total             19954
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b01416_si_002.cif
_cod_data_source_block           ca151117_2_1
_cod_original_cell_volume        9270.2(2)
_cod_database_code               4132078
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C77H54ClIrN2O5P2 (CHCl3)4'
_reflns_odcompleteness_completeness 99.97
_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
 Cl8A-C77 \\sim Cl8-C77 \\sim Cl9A-C77 \\sim Cl9-C77 \\sim Cl4A-C77 \\sim
Cl4-C77
 with sigma of 0.02
 Cl4-Cl8 \\sim Cl8-Cl9 \\sim Cl9-Cl4 \\sim Cl4A-Cl8A \\sim Cl8A-Cl9A \\sim
Cl9A-Cl4A
 with sigma of 0.02
 C76A-C73 \\sim C76-C73
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C82) = Uanis(C82A)
Uanis(C88) = Uanis(C88A)
Uanis(C89) = Uanis(C89A)
Uanis(C87) = Uanis(C87A)
Uanis(C80) = Uanis(C80A)
Uanis(C76) = Uanis(C76A)
4. Rigid body (RIGU) restrains
 C77, Cl4, Cl8, Cl9, Cl8A, Cl9A, Cl4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C76, C80, C82, C87, C88, C89, C76A, C82A, C87A, C88A, C89A, C73, C80A, O5, O7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H73A)=Sof(H77A)=Sof(Cl8A)=Sof(Cl9A)=Sof(Cl4A)=Sof(C76A)=Sof(C82A)=
 Sof(H82A)=Sof(C88A)=Sof(H88A)=Sof(C89A)=Sof(H89A)=Sof(C87A)=Sof(H87A)=
 Sof(C80A)=Sof(H80A)=1-FVAR(1)
 Sof(Cl4)=Sof(Cl8)=Sof(Cl9)=Sof(H73)=Sof(C76)=Sof(C82)=Sof(H82)=Sof(C88)=
 Sof(H88)=Sof(C89)=Sof(H89)=Sof(C87)=Sof(H87)=Sof(C80)=Sof(H80)=Sof(H77)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C22(H22), C52(H52), C73(H73), C73(H73A), C75(H75), C77(H77), C77(H77A),
 C79(H79), C85(H85)
6.b Secondary CH2 refined with riding coordinates:
 C64(H64A,H64B)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C6(H6), C13(H13), C17(H17), C19(H19), C20(H20), C21(H21), C23(H23),
 C24(H24), C26(H26), C27(H27), C28(H28), C31(H31), C32(H32), C33(H33), C36(H36),
  C38(H38), C39(H39), C40(H40), C42(H42), C43(H43), C44(H44), C45(H45),
 C46(H46), C47(H47), C48(H48), C49(H49), C50(H50), C53(H53), C54(H54), C56(H56),
  C57(H57), C58(H58), C59(H59), C61(H61), C62(H62), C63(H63), C66(H66),
 C68(H68), C70(H70), C71(H71), C72(H72), C74(H74), C82(H82), C88(H88), C89(H89),
  C87(H87), C80(H80), C82A(H82A), C88A(H88A), C89A(H89A), C87A(H87A), C80A(H80A)
6.d Fitted hexagon refined as free rotating group:
 C76(C82,C88,C89,C87,C80), C76A(C82A,C88A,C89A,C87A,C80A)
6.e Idealised Me refined as rotating group:
 C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C86(H86A,H86B,H86C)
;
_shelx_res_checksum              56381
_shelx_hkl_checksum              63128
_shelx_fab_checksum              5350
_olex2_date_sample_data_collection 2017-11-16
_olex2_date_sample_submission    2017-11-15
_olex2_submission_original_sample_id ca151117_2_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 1.360
_oxdiff_exptl_absorpt_empirical_full_min 0.804