Scope and Mechanism of the Redox-Active 1,2-Benzoquinone Enabled Ruthenium-Catalyzed Deaminative α-Alkylation of Ketones with Amines
Kirinde Arachchige, Pandula T.; Handunneththige, Suhashini; Talipov, Marat R.; Kalutharage, Nishantha; Yi, Chae S.; ACS Catalysis 11 (2021) 13962–13972; doi:10.1021/acscatal.1c04732

data_4519181
_publ_section_title
;
 Scope and Mechanism of the Redox-Active 1,2-Benzoquinone Enabled
 Ruthenium-Catalyzed Deaminative \a-Alkylation of Ketones with Amines
;
_journal_issue                   22
_journal_name_full               'ACS Catalysis'
_journal_page_first              13962
_journal_page_last               13972
_journal_paper_doi               10.1021/acscatal.1c04732
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C51 H86 O3 P2 Ru'
_chemical_formula_sum            'C51 H86 O3 P2 Ru'
_chemical_formula_weight         910.20
_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     iterative
_audit_creation_date             2019-11-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.3343(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.07721(19)
_cell_length_b                   13.38539(14)
_cell_length_c                   17.77134(18)
_cell_measurement_reflns_used    20355
_cell_measurement_temperature    100.3(9)
_cell_measurement_theta_max      70.5880
_cell_measurement_theta_min      3.9220
_cell_volume                     4775.81(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.3(9)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3756
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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   -117.00 -18.00   1.00    3.00    --  -42.58 -37.00 120.00   99
  2  \w    -93.00  -2.00   1.00    3.00    --  -42.58 125.00 -60.00   91
  3  \w    -67.00  32.00   1.00    3.00    --  -42.58  37.00-120.00   99
  4  \w     67.00 176.00   1.00   12.00    --  100.00  77.00   0.00  109
  5  \w     27.00 118.00   1.00   12.00    --  100.00-125.00 -30.00   91
  6  \w     24.00 133.00   1.00   12.00    --  100.00 -77.00 120.00  109
  7  \w     71.00 172.00   1.00   12.00    --  100.00  61.00-120.00  101
  8  \w     17.00 110.00   1.00   12.00    --  100.00 -94.00 -30.00   93
  9  \w     22.00 111.00   1.00   12.00    --  100.00-107.00-115.00   89
 10  \w     94.00 173.00   1.00   12.00    --  100.00 125.00  90.00   79
 11  \w     94.00 173.00   1.00   12.00    --  100.00 125.00-180.00   79
 12  \w   -115.00 -14.00   1.00    3.00    --  -42.58 -57.00 -90.00  101
 13  \w   -119.00 -10.00   1.00    3.00    --  -42.58 -77.00-120.00  109
 14  \w   -115.00 -14.00   1.00    3.00    --  -42.58 -57.00  30.00  101
 15  \w     71.00 100.00   1.00   12.00    --  100.00  61.00 -60.00   29
 16  \w     47.00 178.00   1.00   12.00    --  100.00  15.00 150.00  131
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0010293000
_diffrn_orient_matrix_UB_12      0.0445384000
_diffrn_orient_matrix_UB_13      -0.0799636000
_diffrn_orient_matrix_UB_21      0.0193940000
_diffrn_orient_matrix_UB_22      -0.1025643000
_diffrn_orient_matrix_UB_23      -0.0325610000
_diffrn_orient_matrix_UB_31      -0.0742036000
_diffrn_orient_matrix_UB_32      -0.0274018000
_diffrn_orient_matrix_UB_33      -0.0078873000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            44427
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        70.563
_diffrn_reflns_theta_max         70.563
_diffrn_reflns_theta_min         3.969
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.586
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.512
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       prism
_exptl_crystal_F_000             1960
_exptl_crystal_size_max          0.215
_exptl_crystal_size_mid          0.183
_exptl_crystal_size_min          0.116
_refine_diff_density_max         0.866
_refine_diff_density_min         -0.551
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     520
_refine_ls_number_reflns         9074
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0358
_refine_ls_R_factor_gt           0.0319
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0496P)^2^+2.7976P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0821
_refine_ls_wR_factor_ref         0.0856
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8218
_reflns_number_total             9074
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04732_si_004.cif
_cod_data_source_block           yi4z
_cod_database_code               4519181
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'Ru (P C18 H33)2 C15 H22 O3'
_reflns_odcompleteness_completeness 99.93
_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.a Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C13(H13), C19(H19), C25(H25), C31(H31)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C14(H14A,H14B),
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B),
  C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C26(H26A,
 H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B),
 C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B)
2.c Aromatic/amide H refined with riding coordinates:
 C40(H40), C42(H42)
2.d Idealised Me refined as rotating group:
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,
 H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C)
;
_olex2_date_sample_submission    2019-11-25
_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 1.274
_oxdiff_exptl_absorpt_empirical_full_min 0.741