Highly Productive α-Alkylation of Ketones with Alcohols Mediated by an Ir‒Oxalamidato/Solid Base Catalyst System
Shimizu, Hideo; Maeda, Hironori; Nara, Hideki; Organic Process Research & Development  (2020) –; doi:10.1021/acs.oprd.0c00362

data_1559089
_publ_section_title
;
 Highly Productive \a-Alkylation of Ketones with Alcohols Mediated by an
 Ir--Oxalamidato/Solid Base Catalyst System
;
_journal_name_full               'Organic Process Research &amp; Development'
_journal_paper_doi               10.1021/acs.oprd.0c00362
_journal_year                    2020
_chemical_formula_moiety         'C22 H30 Cl Ir N O'
_chemical_formula_sum            'C22 H30 Cl Ir N O'
_chemical_formula_weight         552.12
_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     direct
_audit_creation_date             2020-01-09
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.05 svn.r3537 for Rigaku Oxford Diffraction, GUI svn.r5625)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.795(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4344(2)
_cell_length_b                   12.4456(3)
_cell_length_c                   16.3498(4)
_cell_measurement_reflns_used    13668
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      30.0380
_cell_measurement_theta_min      1.9690
_cell_volume                     2108.31(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.787
_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    -18.00  66.00   0.50    1.38    --   -3.65  44.00  58.00  168
  2  \w     24.00  50.00   0.50    1.38    --   -3.65  37.00 -90.00   52
  3  \w    -26.00   9.00   0.50    1.38    --   -3.65 -99.00-150.00   70
  4  \w    -26.00  20.00   0.50    1.38    --    3.81 -99.00 -90.00   92
  5  \w    -72.00  12.00   0.50    1.38    --   -3.65 -44.00 -92.00  168
  6  \w    -40.00 -14.00   0.50    0.10    --   -4.28 -44.00 -92.00   52
  7  \w    -26.00  -1.00   0.50    0.10    --   -4.28 -99.00-180.00   50
  8  \w    -71.00 -46.00   0.50    0.10    --    4.44 -19.00 -30.00   50
  9  \w    -48.00 -23.00   0.50    0.10    --    4.44 -44.00 -92.00   50
 10  \w    -20.00  69.00   0.50    0.10    --   -4.28  57.00 -30.00  178
 11  \w    -71.00 -46.00   0.50    0.10    --    4.44 -19.00-180.00   50
 12  \w      0.00  25.00   0.50    0.10    --   -4.28  44.00  58.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0060955000
_diffrn_orient_matrix_UB_12      0.0296835000
_diffrn_orient_matrix_UB_13      -0.0373087000
_diffrn_orient_matrix_UB_21      0.0661659000
_diffrn_orient_matrix_UB_22      -0.0091609000
_diffrn_orient_matrix_UB_23      -0.0036948000
_diffrn_orient_matrix_UB_31      -0.0164875000
_diffrn_orient_matrix_UB_32      -0.0477815000
_diffrn_orient_matrix_UB_33      -0.0224247000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0400
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.787
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            18580
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.787
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.145
_diffrn_reflns_theta_min         1.966
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.470
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79137
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.37a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.739
_exptl_crystal_description       block
_exptl_crystal_F_000             1084
_exptl_crystal_size_max          0.235
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.101
_refine_diff_density_max         0.981
_refine_diff_density_min         -0.841
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     244
_refine_ls_number_reflns         4901
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0253
_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^)+(0.0195P)^2^+3.1229P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0535
_refine_ls_wR_factor_ref         0.0561
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4197
_reflns_number_total             4901
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            op0c00362_si_002.cif
_cod_data_source_block           exp_71
_cod_database_code               1559089
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_frames
;
019861422da3d3d0b53bbb1c8b78194c4b010300afe
;
_diffrn_oxdiff_digest_hkl
;
01099ebd4fe8daa6f3612c7fe6904b25206ab8
;
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C2AA(H2AA), C1AA(H1AA)
2.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C19(H19A,H19B,
 H19C), C4(H4A,H4B,H4C), C0BA(H0BA,H0BB,H0BC), C9AA(H9AA,H9AB,H9AC), C7AA(H7AA,
 H7AB,H7AC), C8AA(H8AA,H8AB,H8AC)
;
_shelx_res_checksum              97779
_shelx_hkl_checksum              90649
_ins_header
;
TITL exp_71 in P2(1)/c 
REM P2(1)/c (#14 in standard setting)
CELL 0.71073  10.434360  12.445560  16.349793  90.0000  96.7947  90.0000
ZERR    2.00   0.000224   0.000269   0.000388   0.0000   0.0021   0.0000
LATT  1
SYMM -x, y+1/2,-z+1/2 
SFAC C H N O Cl Ir
UNIT 88.00 120.00 4.00 4.00 4.00 2.00
TREF
HKLF 4
END
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_diffrn_reflns_filtered   16588
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.183
_oxdiff_exptl_absorpt_empirical_full_min 0.892