Catalyst-Controlled Regioselective Carbonylation of Isobutylene Oxide to Pivalolactone
Hubbell, Aran K.; Lamb, Jessica R.; Klimovica, Kristine; Mulzer, Michael; Shaffer, Timothy D.; MacMillan, Samantha N.; Coates, Geoffrey W.; ACS Catalysis  (2020) 12537–12543; doi:10.1021/acscatal.0c03492

data_4518133
_publ_section_title
;
 Catalyst-Controlled Regioselective Carbonylation of Isobutylene Oxide to
 Pivalolactone
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              12537
_journal_page_last               12543
_journal_paper_doi               10.1021/acscatal.0c03492
_journal_year                    2020
_chemical_formula_moiety
'C54 H34 Al Cl N2 O2, 2(C H Cl3), C0.59 H0.59 Cl1.59, C0.41 H0.41 Cl1.41'
_chemical_formula_sum            'C57 H37 Al Cl10 N2 O2'
_chemical_formula_weight         1163.36
_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             2017-06-19
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2016.08.26 svn.r3337 for Rigaku Oxford Diffraction, GUI svn.r5221)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.8410(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.23600(10)
_cell_length_b                   21.43260(10)
_cell_length_c                   20.17230(10)
_cell_measurement_reflns_used    35118
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.6170
_cell_measurement_theta_min      3.0370
_cell_volume                     5136.56(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_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    -22.00   3.00   0.50    1.00    --   48.05 -47.00  56.00   50
  2  \w     31.00  94.00   0.50    1.00    --   48.05-125.00  90.00  126
  3  \w     39.00  66.00   0.50    1.00    --   48.05-125.00  60.00   54
  4  \w     88.00 119.00   0.50    3.00    --  107.75 -47.00  56.00   62
  5  \w    101.00 160.00   0.50    3.00    --  107.75  30.00   0.00  118
  6  \w     93.00 123.00   0.50    3.00    --  107.75  77.00-120.00   60
  7  \w    148.00 174.00   0.50    3.00    --  107.75  47.00-154.00   52
  8  \w    144.00 177.00   0.50    3.00    --  107.75  77.00-120.00   66
  9  \w    112.00 177.00   0.50    3.00    --  107.75  45.00-180.00  130
 10  \w     99.00 147.00   0.50    3.00    --  107.75  30.00-150.00   96
 11  \w     86.00 163.00   0.50    3.00    --  107.75   0.00-180.00  154
 12  \w     89.00 116.00   0.50    3.00    --  107.75 -30.00-150.00   54
 13  \w     60.00  85.00   0.50    3.00    --  107.75 -30.00-150.00   50
 14  \w     77.00 118.00   0.50    3.00    --  107.75 -45.00 -60.00   82
 15  \w     57.00  85.00   0.50    3.00    --  107.75 -47.00  56.00   56
 16  \w     37.00 118.00   0.50    3.00    --  107.75 -61.00  60.00  162
 17  \w     47.00 120.00   0.50    3.00    --  107.75-125.00  30.00  146
 18  \w     37.00 103.00   0.50    3.00    --  107.75 -94.00 -60.00  132
 19  \w     38.00  79.00   0.50    3.00    --  107.75   0.00-180.00   82
 20  \w     34.00 111.00   0.50    3.00    --  107.75 -15.00-150.00  154
 21  \w     49.00  85.00   0.50    1.00    --   48.05  47.00-154.00   72
 22  \w     38.00 103.00   0.50    3.00    --  107.75 -94.00-120.00  130
 23  \w    -50.00  24.00   0.50    1.00    --  -48.05  47.00-154.00  148
 24  \w   -105.00 -71.00   0.50    1.00    --  -48.05-125.00-150.00   68
 25  \w   -106.00 -70.00   0.50    1.00    --  -48.05-125.00-120.00   72
 26  \w   -120.00 -48.00   0.50    1.00    --  -48.05 -47.00  56.00  144
 27  \w   -140.00-115.00   0.50    3.00    --  -86.25 -47.00  56.00   50
 28  \w    -56.00 -31.00   0.50    3.00    --  -86.25  47.00-154.00   50
;
_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      0.1158247000
_diffrn_orient_matrix_UB_12      -0.0273519000
_diffrn_orient_matrix_UB_13      0.0350856000
_diffrn_orient_matrix_UB_21      -0.0071449000
_diffrn_orient_matrix_UB_22      0.0313248000
_diffrn_orient_matrix_UB_23      0.0675960000
_diffrn_orient_matrix_UB_31      -0.0578164000
_diffrn_orient_matrix_UB_32      -0.0586246000
_diffrn_orient_matrix_UB_33      0.0197184000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0251
_diffrn_reflns_av_unetI/netI     0.0191
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            46691
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.070
_diffrn_reflns_theta_min         3.056
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.507
_exptl_absorpt_correction_T_max  0.833
_exptl_absorpt_correction_T_min  0.379
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.27b (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            'metallic yellow'
_exptl_crystal_density_diffrn    1.504
_exptl_crystal_description       plate
_exptl_crystal_F_000             2368
_exptl_crystal_size_max          0.319
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.053
_refine_diff_density_max         0.835
_refine_diff_density_min         -0.726
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     686
_refine_ls_number_reflns         9742
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0366
_refine_ls_R_factor_gt           0.0352
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0503P)^2^+4.6975P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0953
_refine_ls_wR_factor_ref         0.0962
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9278
_reflns_number_total             9742
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c03492_si_001.cif
_cod_data_source_block           rkk1_abs
_cod_database_code               4518133
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C57H37AlCl10N2O2
_chemical_oxdiff_usercomment     'Crystallized from chloroform'
_reflns_odcompleteness_completeness 99.65
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Others
 Sof(Cl10)=Sof(Cl9B)=Sof(Cl11)=Sof(C57B)=Sof(H57B)=1-FVAR(1)
 Sof(Cl8A)=Sof(Cl9A)=Sof(C57A)=Sof(H57A)=Sof(Cl8B)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C55(H55), C56(H56), C57A(H57A), C57B(H57B)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C12(H12),
 C13(H13), C17(H17), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C25(H25),
  C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C36(H36), C38(H38),
 C40(H40), C41(H41), C43(H43), C44(H44), C45(H45), C50(H50), C51(H51), C52(H52),
  C53(H53), C54(H54)
;
_shelx_res_checksum              52278
_shelx_hkl_checksum              64814
_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 1.882
_oxdiff_exptl_absorpt_empirical_full_min 0.822