Synthesis of Sterically Hindered β-Diketones via Condensation of Acid Chlorides with Enolates.
Crossman, Aaron S.; Larson, Alec T.; Shi, Jake X.; Krajewski, Sebastian M.; Akturk, Eser S.; Marshak, Michael P.; The Journal of organic chemistry 84 (2019) 7434–7442; doi:10.1021/acs.joc.9b00433

data_4034584
_publ_section_title
;
 Synthesis of Sterically Hindered \b-Diketones via Condensation of Acid
 Chlorides with Enolates.
;
_journal_issue                   11
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7434
_journal_page_last               7442
_journal_paper_doi               10.1021/acs.joc.9b00433
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C59 H76 O2'
_chemical_formula_sum            'C59 H76 O2'
_chemical_formula_weight         817.19
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-21
_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
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1187(2)
_cell_length_b                   21.3827(5)
_cell_length_c                   23.1950(6)
_cell_measurement_reflns_used    9887
_cell_measurement_temperature    102(2)
_cell_measurement_theta_max      30.74
_cell_measurement_theta_min      2.77
_cell_volume                     5018.6(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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_temperature      102.49
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0567
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            37404
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.604
_diffrn_reflns_theta_min         2.591
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.063
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.6946
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0460 before and 0.0422 after correction. The Ratio of minimum to maximum transmission is 0.9308. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.082
_exptl_crystal_description       block
_exptl_crystal_F_000             1784
_exptl_crystal_size_max          0.518
_exptl_crystal_size_mid          0.384
_exptl_crystal_size_min          0.268
_refine_diff_density_max         0.581
_refine_diff_density_min         -0.268
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 5088 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.4(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     593
_refine_ls_number_reflns         16586
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0668
_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^)+(0.0630P)^2^+0.4419P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1066
_refine_ls_wR_factor_ref         0.1165
_reflns_Friedel_coverage         0.811
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                13473
_reflns_number_total             16586
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00433_si_002.cif
_cod_data_source_block           tripph5h
_cod_database_code               4034584
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.968
_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. Restrained distances
 H1-O1
 0.84 with sigma of 0.02
3. Others
 Sof(H19A)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21B)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(H19)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21A)=Sof(H21A)=
 Sof(H21B)=Sof(H21C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C19(H19A), C22(H22), C31(H31), C34(H34), C37(H37)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C7(H7), C8(H8), C12(H12), C14(H14), C27(H27), C29(H29),
 C41(H41), C42(H42), C43(H43), C44(H44), C47(H47), C49(H49), C51(H51)
4.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C57(H57A,H57B,H57C), C58(H58A,H58B,
 H58C), C59(H59A,H59B,H59C), C20A(H20A,H20B,H20C), C21A(H21A,H21B,H21C),
 C20B(H20D,H20E,H20F), C21B(H21D,H21E,H21F)
;
_shelx_res_checksum              12084
_olex2_submission_special_instructions 'No special instructions were received'