Deoxygenative α-Alkylation and α-Arylation of 1,2-Dicarbonyls
Jin, Shengfei; Dang, Hang T.; Haug, Graham C.; Nguyen, Viet D.; Arman, Hadi; Larionov, Oleg V.; Chemical Science  (2020) –; doi:10.1039/D0SC03118F

data_1558465
_publ_section_title
;
 Deoxygenative \a-Alkylation and \a-Arylation of 1,2-Dicarbonyls
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03118F
_journal_year                    2020
_chemical_formula_moiety         'C28 H47 B N3 O2 P'
_chemical_formula_sum            'C28 H47 B N3 O2 P'
_chemical_formula_weight         499.46
_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             2020-03-16
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.10.09 svn.r3662 for Rigaku Oxford Diffraction, GUI svn.r5959)
;
_audit_update_record
;
2020-03-27 deposited with the CCDC.	2020-07-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.889(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.3547(2)
_cell_length_b                   17.4727(4)
_cell_length_c                   14.7370(2)
_cell_measurement_reflns_used    11295
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3400
_cell_measurement_theta_min      3.9410
_cell_volume                     2880.34(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.956
_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     31.00 120.00   0.50    0.40    --   46.62  55.00 -28.62  178
  2  \w     81.00 169.00   0.50    1.60    --  106.69 146.00-172.00  176
  3  \w     91.00 178.00   0.50    1.60    --  106.69  30.00 120.00  174
  4  \w     46.00 127.00   0.50    1.60    --  106.69-146.00 136.00  162
  5  \w     46.00 108.00   0.50    0.40    --   46.62-146.00 136.00  124
  6  \w     34.00 101.00   0.50    1.60    --  106.69 -77.00  90.00  134
  7  \w     34.00  71.00   0.50    1.60    --  106.69 -61.00  90.00   74
  8  \w     34.00  71.00   0.50    1.60    --  106.69 -61.00 120.00   74
  9  \w     34.00  95.00   0.50    0.40    --   46.62-124.00 -57.00  122
 10  \w     34.00 111.00   0.50    1.60    --  106.69-124.00 -57.00  154
 11  \w     34.00  71.00   0.50    1.60    --  106.69 -61.00 -60.00   74
 12  \w     34.00 101.00   0.50    1.60    --  106.69 -77.00 -60.00  134
 13  \w     34.00 105.00   0.50    1.60    --  106.69 -94.00 -60.00  142
 14  \w     34.00  71.00   0.50    1.60    --  106.69 -61.00-180.00   74
 15  \w    -85.00 -12.00   0.50    0.40    --  -46.62 124.00  21.00  146
 16  \w    -51.00 -16.00   0.50    1.60    --  -88.50  45.00-180.00   70
 17  \w    -51.00 -16.00   0.50    1.60    --  -88.50  45.00-150.00   70
 18  \w    -51.00 -16.00   0.50    1.60    --  -88.50  45.00-120.00   70
 19  \w    -51.00 -16.00   0.50    1.60    --  -88.50  45.00 -60.00   70
 20  \w   -102.00 -24.00   0.50    1.60    --  -88.50 146.00-172.00  156
 21  \w   -119.00 -83.00   0.50    0.40    --  -46.62 -57.00 120.00   72
 22  \w   -119.00 -83.00   0.50    0.40    --  -46.62 -57.00 150.00   72
 23  \w   -119.00 -87.00   0.50    0.40    --  -46.62-125.00  60.00   64
 24  \w   -119.00 -59.00   0.50    0.40    --  -46.62-146.00 136.00  120
 25  \w   -160.00 -74.00   0.50    1.60    --  -88.50-124.00 -57.00  172
 26  \w   -119.00 -83.00   0.50    0.40    --  -46.62 -57.00-150.00   72
 27  \w   -119.00 -83.00   0.50    0.40    --  -46.62 -57.00-180.00   72
 28  \w   -119.00 -83.00   0.50    0.40    --  -46.62 -57.00 -90.00   72
 29  \w   -160.00-101.00   0.50    1.60    --  -88.50 -77.00  60.00  118
 30  \w    -51.00 -16.00   0.50    1.60    --  -88.50  45.00 150.00   70
 31  \w    -71.00 -15.00   0.50    1.60    --  -88.50  61.00 120.00  112
;
_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      0.0399995000
_diffrn_orient_matrix_UB_12      -0.0836636000
_diffrn_orient_matrix_UB_13      0.0195920000
_diffrn_orient_matrix_UB_21      0.1285665000
_diffrn_orient_matrix_UB_22      0.0272925000
_diffrn_orient_matrix_UB_23      0.0349577000
_diffrn_orient_matrix_UB_31      -0.0283113000
_diffrn_orient_matrix_UB_32      0.0069478000
_diffrn_orient_matrix_UB_33      0.0982160000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0396
_diffrn_reflns_av_unetI/netI     0.0281
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            32219
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.534
_diffrn_reflns_theta_min         3.952
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.055
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.513
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.63a (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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.152
_exptl_crystal_description       plank
_exptl_crystal_F_000             1088
_exptl_crystal_size_max          0.257
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.049
_refine_diff_density_max         0.338
_refine_diff_density_min         -0.495
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         5795
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0466
_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^)+(0.0500P)^2^+2.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1124
_refine_ls_wR_factor_ref         0.1165
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5058
_reflns_number_total             5795
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03118f2.cif
_cod_data_source_block           hpd107
_cod_database_code               1558465
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H20N2O4
_chemical_oxdiff_usercomment     'air sensitive sample'
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.773
_reflns_odcompleteness_completeness 99.94
_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 Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C23(H23A,H23B), C27(H27A,H27B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C6(H6), C4(H4), C11(H11), C15(H15), C12(H12), C14(H14)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C8(H8A,H8B,H8C), C22(H22A,H22B,H22C), C19(H19A,H19B,
 H19C), C21(H21A,H21B,H21C), C18(H18A,H18B,H18C), C16(H16A,H16B,H16C), C26(H26A,
 H26B,H26C), C24(H24A,H24B,H24C), C20(H20A,H20B,H20C), C28(H28A,H28B,H28C)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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 1.223
_oxdiff_exptl_absorpt_empirical_full_min 0.792