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_1559090
_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 O2'
_chemical_formula_sum            'C22 H30 Cl Ir N O2'
_chemical_formula_weight         568.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_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                 96.471(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6176(2)
_cell_length_b                   9.8322(3)
_cell_length_c                   26.3480(8)
_cell_measurement_reflns_used    9335
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.5760
_cell_measurement_theta_min      2.4210
_cell_volume                     2218.24(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.57a (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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.783
_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      1.00  53.00   0.50    5.18    --   -3.73  47.00 -55.00  104
  2  \w    -23.00  31.00   0.50    5.18    --   -3.73 -99.00-150.00  108
  3  \w    -21.00  23.00   0.50    5.18    --   -3.73 -99.00 -90.00   88
  4  \w    -72.00   3.00   0.50    5.18    --    3.73 -19.00 120.00  150
  5  \w    -23.00  31.00   0.50    5.18    --   -3.73 -99.00 150.00  108
  6  \w    -56.00 -31.00   0.50    5.18    --   -3.73 -47.00 155.00   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      0.0730789000
_diffrn_orient_matrix_UB_12      -0.0272500000
_diffrn_orient_matrix_UB_13      -0.0048866000
_diffrn_orient_matrix_UB_21      0.0078598000
_diffrn_orient_matrix_UB_22      -0.0320978000
_diffrn_orient_matrix_UB_23      0.0242765000
_diffrn_orient_matrix_UB_31      -0.0382551000
_diffrn_orient_matrix_UB_32      -0.0585529000
_diffrn_orient_matrix_UB_33      -0.0109960000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0584
_diffrn_reflns_av_unetI/netI     0.0502
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.783
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            21492
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.783
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.260
_diffrn_reflns_theta_min         2.213
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.155
_exptl_absorpt_correction_T_max  0.920
_exptl_absorpt_correction_T_min  0.306
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.57a (Rigaku Oxford Diffraction, 2019)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.701
_exptl_crystal_description       prism
_exptl_crystal_F_000             1116
_exptl_crystal_size_max          0.239
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.133
_refine_diff_density_max         1.616
_refine_diff_density_min         -1.500
_refine_diff_density_rms         0.163
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         5185
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0321
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0243P)^2^+1.6645P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0650
_refine_ls_wR_factor_ref         0.0706
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4352
_reflns_number_total             5185
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            op0c00362_si_003.cif
_cod_data_source_block           exp_256
_cod_database_code               1559090
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_frames
;
011f89c6964018c1fc3601ae965a610882006085edf
;
_diffrn_oxdiff_digest_hkl
;
01696057736c75ba21c72877ff6e18bc2fe620
;
_reflns_odcompleteness_completeness 99.93
_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, All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C1AA(H1AA)
2.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C)
2.c Idealised tetrahedral OH refined as rotating group:
 O20(H20)
;
_shelx_res_checksum              49351
_shelx_hkl_checksum              49560
_ins_header
;
TITL exp_256 in P2(1)/n 
REM P2(1)/n (#14 in standard setting)
CELL 0.71073   8.617601   9.832177  26.347962  90.0000  96.4712  90.0000
ZERR    5.00   0.000246   0.000301   0.000763   0.0000   0.0027   0.0000
LATT  1
SYMM -x+1/2, y+1/2,-z+1/2 
SFAC C H N O Cl Ir
UNIT 110.00 150.00 5.00 10.00 5.00 5.00
TREF
HKLF 4
END
;
_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 1.666
_oxdiff_exptl_absorpt_empirical_full_min 0.561