Organocatalytic Decarboxylative Aldol Reaction of β-Ketoacids with α-Ketophosphonates en route for the Enantioselective Synthesis of Tertiary α-Hydroxyphosphonates
Vamisetti, Ganga B.; Chowdhury, Raghunath; Ghosh, Sunil Kumar; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB00796E

data_7155577
_publ_section_title
;
 Organocatalytic Decarboxylative Aldol Reaction of \b-Ketoacids with
 \a-Ketophosphonates en route for the Enantioselective Synthesis of
 Tertiary \a-Hydroxyphosphonates
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB00796E
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H24 Br O5 P'
_chemical_formula_sum            'C16 H24 Br O5 P'
_chemical_formula_weight         407.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-02-10
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2017-02-27 deposited with the CCDC.
2017-04-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.986(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.4281(4)
_cell_length_b                   8.92102(13)
_cell_length_c                   11.7047(2)
_cell_measurement_reflns_used    6833
_cell_measurement_temperature    107.8(4)
_cell_measurement_theta_max      72.9720
_cell_measurement_theta_min      3.9320
_cell_volume                     1950.19(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      107.8(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.1600
_diffrn_detector_type            Titan
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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     20.00 113.00   1.00    1.00    --   43.29  57.00 -30.00   93
  2  \w     75.00 107.00   1.00    1.00    --   43.29 126.00 -60.00   32
  3  \w     72.00 111.00   1.00    1.00    --   43.29 126.00-180.00   39
  4  \w    108.00 155.00   1.00    1.00    --  102.90  77.00-120.00   47
  5  \w    119.00 157.00   1.00    1.00    --  102.90  67.00 -79.44   38
  6  \w    103.00 158.00   1.00    1.00    --  102.90  45.00-150.00   55
  7  \w     97.00 130.00   1.00    1.00    --  102.90 -61.00 -90.00   33
  8  \w     78.00 105.00   1.00    1.00    --  102.90  45.00 -60.00   27
  9  \w     72.00 117.00   1.00    1.00    --  102.90  77.00 -60.00   45
 10  \w     78.00 106.00   1.00    1.00    --  102.90  61.00-120.00   28
 11  \w     71.00 100.00   1.00    1.00    --  102.90  77.00-120.00   29
 12  \w     76.00 103.00   1.00    1.00    --  102.90  61.00 -90.00   27
 13  \w     76.00 108.00   1.00    1.00    --  102.90  61.00 -60.00   32
 14  \w     74.00 100.00   1.00    1.00    --  102.90  67.00 -79.44   26
 15  \w     71.00  97.00   1.00    1.00    --  102.90  77.00-150.00   26
 16  \w     50.00  86.00   1.00    1.00    --   43.29  38.00 -90.00   36
 17  \w    126.00 157.00   1.00    1.00    --  102.90  61.00  60.00   31
 18  \w    101.00 157.00   1.00    1.00    --  102.90 126.00  60.00   56
 19  \w     93.00 145.00   1.00    1.00    --  102.90  77.00  30.00   52
 20  \w     87.00 157.00   1.00    1.00    --  102.90  77.00 150.00   70
 21  \w     77.00 150.00   1.00    1.00    --  102.90  61.00 120.00   73
 22  \w     46.00 127.00   1.00    1.00    --  102.90 -45.00 150.00   81
 23  \w     20.00  71.00   1.00    1.00    --  102.90 -95.00  90.00   51
 24  \w    -24.00  94.00   1.00    1.00    --   43.29   0.00-180.00  118
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Titan'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0108124000
_diffrn_orient_matrix_UB_12      -0.0076764000
_diffrn_orient_matrix_UB_13      -0.1254544000
_diffrn_orient_matrix_UB_21      0.0665802000
_diffrn_orient_matrix_UB_22      0.1010126000
_diffrn_orient_matrix_UB_23      0.0409848000
_diffrn_orient_matrix_UB_31      0.0474792000
_diffrn_orient_matrix_UB_32      -0.1397972000
_diffrn_orient_matrix_UB_33      0.0364496000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0549
_diffrn_reflns_av_unetI/netI     0.0451
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            7048
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.113
_diffrn_reflns_theta_min         3.929
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.826
_exptl_absorpt_correction_T_max  0.415
_exptl_absorpt_correction_T_min  0.213
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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            white
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       block
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.643
_exptl_crystal_size_mid          0.393
_exptl_crystal_size_min          0.366
_refine_diff_density_max         1.316
_refine_diff_density_min         -0.751
_refine_diff_density_rms         0.217
_refine_ls_abs_structure_details
;
 Flack x determined using 1546 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.06(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     214
_refine_ls_number_reflns         3773
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0585
_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^)+(0.1229P)^2^+2.5485P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1480
_refine_ls_wR_factor_ref         0.1709
_reflns_Friedel_coverage         0.837
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.946
_reflns_number_gt                3615
_reflns_number_total             3773
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob00796e4.cif
_cod_data_source_block           raghunath1_1
_cod_database_code               7155577
_chemical_oxdiff_formula         'C16 H24 Br O5 P'
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C5(H5)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2017-02-09
_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 2.559
_oxdiff_exptl_absorpt_empirical_full_min 0.298