Coordination-Induced Stereocontrol over Carbocations: Asymmetric Reductive Deoxygenation of Racemic Tertiary Alcohols.
Isomura, Mayuko; Petrone, David A.; Carreira, Erick M.; Journal of the American Chemical Society 141 (2019) 4738–4748; doi:10.1021/jacs.9b00862

data_4128945
_publ_section_title
;
 Coordination-Induced Stereocontrol over Carbocations: Asymmetric
 Reductive Deoxygenation of Racemic Tertiary Alcohols.
;
_journal_issue                   11
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4738
_journal_page_last               4748
_journal_paper_doi               10.1021/jacs.9b00862
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C85 H60 Cl Ir N2 O5 P2, 2(C H Cl3)'
_chemical_formula_sum            'C87 H62 Cl7 Ir N2 O5 P2'
_chemical_formula_weight         1717.67
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                98.4460(10)
_cell_angle_beta                 92.8420(10)
_cell_angle_gamma                91.7630(10)
_cell_formula_units_Z            2
_cell_length_a                   11.78530(10)
_cell_length_b                   14.6123(2)
_cell_length_c                   22.8572(3)
_cell_measurement_reflns_used    63184
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.2170
_cell_measurement_theta_min      3.3760
_cell_volume                     3885.88(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28d (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (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 0.998
_diffrn_measured_fraction_theta_max 0.973
_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    -47.00  40.00   0.50    2.88    --  -30.00  61.00  43.22  174
  2  \w     53.00  81.00   0.50    2.88    --   30.00  81.00  90.03   56
  3  \w     28.00  60.00   0.50    2.88    --   54.00  82.00  72.29   64
  4  \w     32.00  65.00   0.50    2.88    --   58.00  82.00  92.56   66
  5  \w     62.00  94.00   0.50   10.20    --   82.00  69.00  65.46   64
  6  \w     63.00  92.00   0.50   10.20    --   82.00  66.00  32.71   58
  7  \w    105.00 158.00   0.50   10.20    --   86.00  58.00  23.15  106
  8  \w    143.00 169.00   0.50   10.20    --  102.00  74.00  73.96   52
  9  \w    135.00 173.00   0.50   10.20    --  110.00  77.00   0.00   76
 10  \w    148.00 175.00   0.50   10.20    --  110.00  77.00 -60.00   54
 11  \w    140.00 177.00   0.50   10.20    --  110.00 125.00 -30.00   74
 12  \w    121.00 167.00   0.50   10.20    --  110.00  77.00  30.00   92
 13  \w    120.00 150.00   0.50   10.20    --   86.00  76.00 116.26   60
 14  \w    109.00 153.00   0.50   10.20    --   86.00  80.00 164.67   88
 15  \w     96.00 158.00   0.50   10.20    --  110.00  57.00 120.00  124
 16  \w     92.00 129.00   0.50   10.20    --  110.00  77.00   0.00   74
 17  \w     95.00 173.00   0.50   10.20    --  110.00  57.00 -60.00  156
 18  \w    127.00 155.00   0.50   10.20    --   90.00  63.00-161.03   56
 19  \w    138.00 172.00   0.50   10.20    --  110.00  77.00-180.00   68
 20  \w    136.00 166.00   0.50   10.20    --  110.00  77.00-150.00   60
 21  \w     98.00 146.00   0.50   10.20    --  110.00  38.00-120.00   96
 22  \w     86.00 172.00   0.50   10.20    --  110.00  77.00 -90.00  172
 23  \w    104.00 131.00   0.50   10.20    --  110.00 125.00 -30.00   54
 24  \w     87.00 117.00   0.50   10.20    --  110.00  77.00  30.00   60
 25  \w     94.00 168.00   0.50   10.20    --  110.00  57.00  60.00  148
 26  \w     87.00 168.00   0.50   10.20    --  110.00  77.00 150.00  162
 27  \w     86.00 175.00   0.50   10.20    --  110.00  77.00 120.00  178
 28  \w     80.00 130.00   0.50   10.20    --  102.00  74.00  73.96  100
 29  \w     86.00 176.00   0.50   10.20    --  110.00  77.00  90.00  180
 30  \w     86.00 176.00   0.50   10.20    --  110.00  77.00 -30.00  180
 31  \w     87.00 131.00   0.50   10.20    --  110.00  77.00-180.00   88
 32  \w     88.00 172.00   0.50   10.20    --  110.00  77.00-120.00  168
 33  \w     86.00 113.00   0.50   10.20    --  110.00  77.00-150.00   54
 34  \w     70.00 115.00   0.50   10.20    --   86.00  59.00 -80.87   90
 35  \w     87.00 141.00   0.50   10.20    --  110.00  77.00 -60.00  108
 36  \w     72.00 103.00   0.50   10.20    --   90.00  63.00-161.03   62
 37  \w     45.00  77.00   0.50    2.88    --   70.00  83.00-112.42   64
 38  \w     45.00  96.00   0.50    2.88    --   70.00  80.00-143.78  102
 39  \w     52.00 105.00   0.50    2.88    --   78.00  83.00 -28.70  106
 40  \w     70.00 103.00   0.50   10.20    --   86.00  58.00  23.15   66
 41  \w     69.00 101.00   0.50   10.20    --   86.00  62.00  38.44   64
 42  \w     63.00  95.00   0.50   10.20    --   86.00  76.00 116.26   64
 43  \w     61.00  88.00   0.50   10.20    --   82.00  70.00 157.36   54
 44  \w     61.00  99.00   0.50   10.20    --   86.00  80.00 164.67   76
 45  \w     28.00  56.00   0.50    2.88    --   54.00  82.00 165.41   56
 46  \w      5.00  39.00   0.50    2.88    --   30.00  81.00  90.03   68
 47  \w     20.00  45.00   0.50    2.88    --   50.00  90.00 -22.96   50
 48  \w     20.00  45.00   0.50    2.88    --   50.00  90.00-121.23   50
 49  \w     42.00  83.00   0.50   10.20    --  110.00 -57.00  60.00   82
 50  \w     47.00 108.00   0.50   10.20    --  110.00 -99.00  30.00  122
 51  \w     78.00 109.00   0.50   10.20    --  110.00 -99.00 -60.00   62
 52  \w    108.00 133.00   0.50   10.20    --  110.00 -77.00 -60.00   50
 53  \w     75.00 122.00   0.50   10.20    --  110.00-125.00-120.00   94
 54  \w     63.00 121.00   0.50    2.88    --   49.37-178.00-150.00  116
 55  \w     44.00  92.00   0.50   10.20    --  110.00 -77.00 -60.00   96
 56  \w     40.00  75.00   0.50   10.20    --  110.00 -99.00 -60.00   70
 57  \w     46.00  92.00   0.50   10.20    --  110.00 -99.00 -90.00   92
 58  \w     40.00 106.00   0.50   10.20    --  110.00 -99.00  90.00  132
 59  \w     49.00  84.00   0.50   10.20    --  110.00 -57.00 120.00   70
 60  \w     55.00  92.00   0.50   10.20    --  110.00 -99.00 150.00   74
 61  \w    -68.00 -38.00   0.50    2.88    --  -49.37 -57.00  90.00   60
 62  \w    -72.00 -43.00   0.50    2.88    --  -49.37 -38.00 150.00   58
 63  \w    -72.00 -45.00   0.50   10.20    --  -70.00 -79.00  97.19   54
 64  \w    -70.00 -44.00   0.50   10.20    --  -70.00 -81.00  67.87   52
 65  \w    -74.00 -44.00   0.50   10.20    --  -70.00 -82.00  20.58   60
 66  \w    -72.00 -34.00   0.50    2.88    --  -49.37 -57.00   0.00   76
 67  \w    -64.00 -38.00   0.50   10.20    --  -62.00 -78.00 -50.71   52
 68  \w    -78.00 -34.00   0.50    2.88    --  -49.37 -57.00 -30.00   88
 69  \w    -72.00 -47.00   0.50   10.20    --  -70.00 -74.00 -17.09   50
 70  \w    -75.00 -46.00   0.50   10.20    --  -70.00 -78.00 -36.14   58
 71  \w    -70.00 -44.00   0.50   10.20    --  -70.00 -82.00 -90.35   52
 72  \w    -72.00 -47.00   0.50   10.20    --  -70.00 -75.00-132.76   50
 73  \w    -76.00 -36.00   0.50    2.88    --  -49.37 -38.00-150.00   80
 74  \w    -80.00 -46.00   0.50   10.20    --  -70.00 -79.00 -76.96   68
 75  \w    -75.00 -43.00   0.50   10.20    --  -70.00 -83.00 -57.43   64
 76  \w    -71.00 -46.00   0.50   10.20    --  -70.00 -78.00  41.30   50
 77  \w    -81.00 -45.00   0.50   10.20    --  -70.00 -80.00 114.98   72
 78  \w    -71.00 -46.00   0.50   10.20    --  -70.00 -78.00 133.66   50
 79  \w    -99.00 -36.00   0.50    2.88    --  -49.37 -38.00   0.00  126
 80  \w   -116.00 -36.00   0.50    2.88    --  -49.37 -38.00 -90.00  160
 81  \w    -70.00 -43.00   0.50   10.20    --  -70.00 -83.00-177.44   54
 82  \w    -80.00 -46.00   0.50   10.20    --  -70.00 -77.00-158.29   68
 83  \w   -125.00 -36.00   0.50    2.88    --  -49.37 -42.00  76.44  178
 84  \w   -125.00 -80.00   0.50    2.88    --  -49.37 -38.00 150.00   90
 85  \w    -87.00 -11.00   0.50   10.20    --  -70.00  77.00 -30.00  152
 86  \w    -91.00 -18.00   0.50   10.20    --  -70.00  77.00-120.00  146
;
_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      -0.0000067000
_diffrn_orient_matrix_UB_12      -0.1064909000
_diffrn_orient_matrix_UB_13      -0.0071620000
_diffrn_orient_matrix_UB_21      -0.1299766000
_diffrn_orient_matrix_UB_22      -0.0035175000
_diffrn_orient_matrix_UB_23      0.0046540000
_diffrn_orient_matrix_UB_31      -0.0161568000
_diffrn_orient_matrix_UB_32      -0.0049592000
_diffrn_orient_matrix_UB_33      -0.0677040000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            33101
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.009
_diffrn_reflns_theta_min         3.060
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.360
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81225
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28d (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_description       plate
_exptl_crystal_F_000             1728
_exptl_crystal_size_max          0.069
_exptl_crystal_size_mid          0.059
_exptl_crystal_size_min          0.014
_refine_diff_density_max         2.561
_refine_diff_density_min         -1.395
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1044
_refine_ls_number_reflns         33101
_refine_ls_number_restraints     313
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0601
_refine_ls_R_factor_gt           0.0532
_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^)+(0.1122P)^2^+2.3890P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1531
_refine_ls_wR_factor_ref         0.1586
_reflns_Friedel_coverage         0.000
_reflns_number_gt                28934
_reflns_number_total             33101
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b00862_si_003.cif
_cod_data_source_block           ca231018_1_1_twin1_hklf4
_cod_database_code               4128945
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C88 H70 Cl Ir N2 O5 P2'
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.668
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7566(5)
 0.2434(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
3. Restrained distances
 H78-H5
 -2.2 with sigma of 0.02
 Cl1A-C1A \\sim Cl1A-C1B \\sim Cl1A-C1C \\sim Cl2A-C1A \\sim Cl3A-C1A \\sim
Cl3B-C1B \\sim Cl2B-C1B ~
 Cl3C-C1C \\sim Cl2C-C1C
 with sigma of 0.02
 Cl1A-Cl2A \\sim Cl2A-Cl3A \\sim Cl3A-Cl1A \\sim Cl1A-Cl2B \\sim Cl2B-Cl3B
\\sim Cl3B-Cl1A \\sim Cl1A-
 Cl2C \\sim Cl2C-Cl3C \\sim Cl3C-Cl1A
 with sigma of 0.02
 Cl1F-Cl2F \\sim Cl2F-Cl3F \\sim Cl3F-Cl1F
 with sigma of 0.02
 Cl2F-C1F \\sim Cl1F-C1F \\sim Cl3F-C1F
 with sigma of 0.02
 Cl1D-C1D \\sim Cl2D-C1D \\sim Cl3D-C1D \\sim Cl1E-C1E \\sim Cl2E-C1E \\sim
Cl3E-C1E
 with sigma of 0.02
 Cl1D-Cl2D \\sim Cl2D-Cl3D \\sim Cl3D-Cl1D \\sim Cl1E-Cl2E \\sim Cl2E-Cl3E
\\sim Cl3E-Cl1E
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(Cl3B) \\sim Ueq, Uanis(Cl3C) \\sim Ueq, Uanis(Cl3A) \\sim Ueq,
Uanis(Cl2B) \\sim Ueq, Uanis(Cl2C) \\sim Ueq, Uanis(Cl2A) \\sim Ueq,
Uanis(Cl1A) \\sim Ueq, Uanis(C1D) \\sim Ueq, Uanis(Cl2D) \\sim Ueq, Uanis(Cl3D)
\\sim Ueq, Uanis(Cl1D) \\sim Ueq, Uanis(C1E) \\sim Ueq, Uanis(Cl1E) \\sim Ueq,
Uanis(Cl2E) \\sim Ueq, Uanis(Cl1F) \\sim Ueq, Uanis(Cl2F) \\sim Ueq, Uanis(C1F)
\\sim Ueq, Uanis(Cl3F) \\sim Ueq, Uanis(Cl3E) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.02
Uanis(C1A) = Uanis(C1C)
Uanis(C1A) = Uanis(C1B)
Uanis(C1D) = Uanis(C1E)
Uanis(Cl2B) = Uanis(Cl2C)
5. Rigid body (RIGU) restrains
 Cl1A, Cl2A, Cl2B, Cl2C, Cl3A, Cl3B, Cl3C, C1A, C1B, C1C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1F, Cl2F, Cl3F, C1F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1E, Cl1E, Cl2E, Cl3E, C1D, Cl1D, Cl2D, Cl3D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(Cl2A)+Sof(Cl3A)+Sof(C1A)+Sof(H1A)+Sof(Cl1D)+Sof(Cl2D)+Sof(Cl3D)+
 Sof(C1D)+Sof(H1D)]+1*[Sof(Cl2B)+Sof(Cl3B)+Sof(C1B)+Sof(H1B)+Sof(Cl1E)+
 Sof(Cl2E)+Sof(C1E)+Sof(H1E)+Sof(Cl3E)]+1*[Sof(Cl2C)+Sof(Cl3C)+Sof(C1C)+
 Sof(H1C)+Sof(Cl1F)+Sof(Cl2F)+Sof(Cl3F)+Sof(C1F)+Sof(H1F)]=1 with esd of 0.0001
 Sof(Cl2A)=Sof(Cl3A)=Sof(C1A)=Sof(H1A)=Sof(Cl1D)=Sof(Cl2D)=Sof(Cl3D)=Sof(C1D)=
 Sof(H1D)=FVAR(1)
 Sof(Cl2B)=Sof(Cl3B)=Sof(C1B)=Sof(H1B)=Sof(Cl1E)=Sof(Cl2E)=Sof(C1E)=Sof(H1E)=
 Sof(Cl3E)=FVAR(2)
 Sof(Cl2C)=Sof(Cl3C)=Sof(C1C)=Sof(H1C)=Sof(Cl1F)=Sof(Cl2F)=Sof(Cl3F)=Sof(C1F)=
 Sof(H1F)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C73(H73), C1A(H1A), C1B(H1B), C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F),
 C19(H19), C20(H20)
7.b Secondary CH2 refined with riding coordinates:
 C71(H71A,H71B), C75(H75A,H75B), C76(H76A,H76B)
7.c Aromatic/amide H refined with riding coordinates:
 C69(H69), C77(H77), C78(H78), C79(H79), C82(H82), C83(H83), C84(H84),
 C85(H85), C1(H1), C7(H7), C8(H8), C10(H10), C14(H14), C15(H15), C17(H17),
 C18(H18), C21(H21), C22(H22), C23(H23), C26(H26), C27(H27), C28(H28), C29(H29),
  C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C40(H40), C42(H42),
 C44(H44), C46(H46), C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54),
  C55(H55), C56(H56), C57(H57), C60(H60), C61(H61), C62(H62), C63(H63),
 C64(H64), C65(H65), C66(H66), C67(H67), C68(H68)
7.d Idealised tetrahedral OH refined as rotating group:
 O5(H5)
;
_shelx_res_checksum              75033
_shelx_hkl_checksum              90972
_olex2_date_sample_data_collection 2018-10-24
_olex2_date_sample_submission    2018-10-23
_olex2_submission_original_sample_id ca231018_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.520
_oxdiff_exptl_absorpt_empirical_full_min 0.728
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by 5.8226\% 
 around [-0.04 0.31 0.95] (reciprocal) or [-0.01 0.69 0.72] (direct)
;