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_1558467
_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_absolute_configuration unk
_chemical_formula_moiety         'C16 H16 O2'
_chemical_formula_sum            'C16 H16 O2'
_chemical_formula_weight         240.29
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-01-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-03-08 deposited with the CCDC.	2020-07-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.910(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.1570(2)
_cell_length_b                   7.4823(2)
_cell_length_c                   11.6050(4)
_cell_measurement_reflns_used    5666
_cell_measurement_temperature    98(2)
_cell_measurement_theta_max      27.0040
_cell_measurement_theta_min      2.7940
_cell_volume                     621.38(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.59a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.59a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.59a (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      98(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -96.00  34.00   1.00   15.00    --   -7.50 -17.00 101.00  130
  2  \w    -49.00  81.00   1.00   15.00    --   -7.50  17.00 -90.00  130
  3  \w    -32.00  81.00   1.00   15.00    --   -7.50  38.00-180.00  113
  4  \w    -96.00  17.00   1.00   15.00    --   -7.50 -38.00 -30.00  113
  5  \w    -26.00  31.00   1.00   15.00    --    4.20  57.00 -60.00   57
  6  \w    -37.00  81.00   1.00   15.00    --   -7.50  57.00  60.00  118
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0650784000
_diffrn_orient_matrix_UB_12      -0.0217834000
_diffrn_orient_matrix_UB_13      0.0432924000
_diffrn_orient_matrix_UB_21      -0.0728149000
_diffrn_orient_matrix_UB_22      -0.0019871000
_diffrn_orient_matrix_UB_23      -0.0421272000
_diffrn_orient_matrix_UB_31      0.0169812000
_diffrn_orient_matrix_UB_32      -0.0922524000
_diffrn_orient_matrix_UB_33      -0.0092817000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0298
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            12259
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.986
_diffrn_reflns_theta_min         2.846
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98773
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.59a (Rigaku Oxford Diffraction, 2019)
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    1.284
_exptl_crystal_description       plate
_exptl_crystal_F_000             256
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.251
_refine_diff_density_min         -0.163
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;

;
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     165
_refine_ls_number_reflns         2413
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0371
_refine_ls_shift/su_max          0.000
_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^+0.1500P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0902
_refine_ls_wR_factor_ref         0.0918
_reflns_Friedel_coverage         0.839
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                2315
_reflns_number_total             2413
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03118f2.cif
_cod_data_source_block           cd1947
_cod_database_code               1558467
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C20H20O2N1
_chemical_oxdiff_usercomment     'Phenyl Ga-51-3'
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.981
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C2(H2), C8(H8), C9(H9), C6(H6), C12(H12), C10(H10), C11(H11)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_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 1.047
_oxdiff_exptl_absorpt_empirical_full_min 0.972