Room-Temperature Coupling/Decarboxylation Reaction of α-Oxocarboxylates with α-Bromoketones: Solvent-Controlled Regioselectivity for 1,2- and 1,3-Diketones.
He, Zhen; Qi, Xiaotian; She, Zhijie; Zhao, Yinsong; Li, Shiqing; Tang, Junbin; Gao, Ge; Lan, Yu; You, Jingsong; The Journal of organic chemistry 82 (2017) 1403–1411; doi:10.1021/acs.joc.6b02575

data_4032338
_publ_section_title
;
 Room-Temperature Coupling/Decarboxylation Reaction of \a-Oxocarboxylates
 with \a-Bromoketones: Solvent-Controlled Regioselectivity for 1,2- and
 1,3-Diketones.
;
_journal_issue                   3
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1403
_journal_page_last               1411
_journal_paper_doi               10.1021/acs.joc.6b02575
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C16 H12 O4, C5 H9 N O'
_chemical_formula_sum            'C21 H21 N O5'
_chemical_formula_weight         367.39
_space_group_crystal_system      monoclinic
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_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-12-30
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;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
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_cell_length_b                   13.2702(3)
_cell_length_c                   14.9401(4)
_cell_measurement_reflns_used    4385
_cell_measurement_temperature    293
_cell_measurement_theta_max      71.9330
_cell_measurement_theta_min      4.5340
_cell_volume                     1930.95(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -99.0000   30.0000 74

  2 omega    7.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   19.0000  -30.0000 101

  3 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000  -30.0000 84

  4 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -99.0000 -120.0000 74

  5 omega  -35.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -19.0000   90.0000 101

  6 omega   23.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921 -125.0000 -150.0000 67

  7 omega   39.00  109.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -180.0000 70

  8 omega   38.00   91.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 53

  9 omega   38.00   91.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 53

 10 omega   38.00   91.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 53

 11 omega   39.00  109.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 70

 12 omega   41.00  126.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000 -150.0000 85

 13 omega   41.00  126.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000  150.0000 85

 14 omega   81.00  176.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 95

 15 omega   57.00  150.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000  150.0000 93

 16 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000 -180.0000 84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0527183000
_diffrn_orient_matrix_UB_12      0.1083155000
_diffrn_orient_matrix_UB_13      0.0040683000
_diffrn_orient_matrix_UB_21      0.1282308000
_diffrn_orient_matrix_UB_22      0.0243346000
_diffrn_orient_matrix_UB_23      0.0807834000
_diffrn_orient_matrix_UB_31      0.0760652000
_diffrn_orient_matrix_UB_32      0.0339843000
_diffrn_orient_matrix_UB_33      -0.0707199000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            10073
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.039
_diffrn_reflns_theta_max         67.039
_diffrn_reflns_theta_min         4.540
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.745
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44515
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_description       block
_exptl_crystal_F_000             776
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_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.461
_refine_diff_density_min         -0.364
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     249
_refine_ls_number_reflns         3436
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0651
_refine_ls_R_factor_gt           0.0578
_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^)+(0.1010P)^2^+0.4490P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1641
_refine_ls_wR_factor_ref         0.1741
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2898
_reflns_number_total             3436
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02575_si_004.cif
_cod_data_source_block           hz-2166
_cod_original_cell_volume        1930.97(9)
_cod_database_code               4032338
_reflns_odcompleteness_completeness 99.89
_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:
 C00B(H00B)
2.b Secondary CH2 refined with riding coordinates:
 C00N(H00A,H00C), C00P(H00D,H00N), C00R(H00S,H00T)
2.c Aromatic/amide H refined with riding coordinates:
 C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H), C00I(H00I), C00J(H00J),
 C00K(H00K), C00L(H00L), C00M(H00M), C00O(H00O)
2.d Idealised Me refined as rotating group:
 C00Q(H00P,H00Q,H00R)
;
_shelx_res_checksum              91697
_shelx_hkl_checksum              75596
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-12-30
_olex2_submission_special_instructions 'No special instructions were received'