Carbonylative, Catalytic Deoxygenation of 2,3-Disubstituted Epoxides with Inversion of Stereochemistry: An Alternative Alkene Isomerization Method.
Lamb, Jessica R.; Hubbell, Aran K.; MacMillan, Samantha N.; Coates, Geoffrey W.; Journal of the American Chemical Society 142 (2020) 8029–8035; doi:10.1021/jacs.0c02653

data_4134757
_publ_section_title
;
 Carbonylative, Catalytic Deoxygenation of 2,3-Disubstituted Epoxides with
 Inversion of Stereochemistry: An Alternative Alkene Isomerization Method.
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8029
_journal_page_last               8035
_journal_paper_doi               10.1021/jacs.0c02653
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety
'2(C36 H50 Al Cl2 N2 O4), 2(C5 Mn O5), 3(C4 H8 O)'
_chemical_formula_sum            'C94 H124 Al2 Cl4 Mn2 N4 O21'
_chemical_formula_weight         1951.60
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-04-26
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6733(3)
_cell_length_b                   23.5355(4)
_cell_length_c                   26.0438(4)
_cell_measurement_reflns_used    26132
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      28.1820
_cell_measurement_theta_min      3.4830
_cell_volume                     9607.0(3)
_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 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -45.00   9.00   0.50   45.00    --    3.71 -90.00  67.00  108
  2  \w    -12.00  23.00   0.50   45.00    --   -4.96 -99.00 150.00   70
  3  \w    -56.00   1.00   0.50   45.00    --   -4.96 -36.00-103.00  114
  4  \w     -9.00  16.00   0.50   45.00    --   -4.96 -99.00-180.00   50
  5  \w    -16.00  10.00   0.50   45.00    --   -4.96 -99.00-120.00   52
;
_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      -0.0336573000
_diffrn_orient_matrix_UB_12      -0.0157344000
_diffrn_orient_matrix_UB_13      0.0113820000
_diffrn_orient_matrix_UB_21      -0.0287643000
_diffrn_orient_matrix_UB_22      0.0224717000
_diffrn_orient_matrix_UB_23      -0.0054760000
_diffrn_orient_matrix_UB_31      -0.0093099000
_diffrn_orient_matrix_UB_32      -0.0125071000
_diffrn_orient_matrix_UB_33      -0.0241257000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0278
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            58659
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.388
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.463
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.518
_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            'clear orange'
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_description       block
_exptl_crystal_F_000             4112
_exptl_crystal_size_max          0.513
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.116
_refine_diff_density_max         1.022
_refine_diff_density_min         -0.587
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.421(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1314
_refine_ls_number_reflns         19346
_refine_ls_number_restraints     1577
_refine_ls_restrained_S_all      1.603
_refine_ls_R_factor_all          0.0450
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0578P)^2^+6.3589P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1021
_refine_ls_wR_factor_ref         0.1044
_reflns_Friedel_coverage         0.846
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                17869
_reflns_number_total             19346
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02653_si_002.cif
_cod_data_source_block           rjrl1_abs
_cod_depositor_comments          'Adding full bibliography for 4134757.cif.'
_cod_database_code               4134757
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C94H124Al2Cl4Mn2N4O21
_chemical_oxdiff_usercomment     'Crystallized from THF'
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.579(17) 0.421(17)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C131-C130 \\sim C35B-C34B \\sim C35A-C34A \\sim C31D_$1-C30C_$1 \\sim
C31C_$1-C30D_$1 ~
 C35D_$1-C34D_$1 \\sim C35C_$1-C34C_$1
 with sigma of 0.02
 O14-C133 \\sim O14-C136 \\sim O13-C129 \\sim O13-C132 \\sim O23_$1-C229_$1
\\sim O23_$1-C232_$1 ~
 O24_$1-C233_$1 \\sim O24_$1-C236_$1
 with sigma of 0.02
 O13-C129 \\sim O13-C132 \\sim O14-C133 \\sim O14-C136 \\sim O24_$1-C233_$1
\\sim O24_$1-C236_$1 ~
 O23_$1-C229_$1 \\sim O23_$1-C232_$1
 with sigma of 0.02
 C132-C131 \\sim C130-C129 \\sim C34A-C133 \\sim C34B-C133 \\sim C35A-C136
\\sim C35B-C136 ~
 C34D_$1-C233_$1 \\sim C34C_$1-C233_$1 \\sim C35C_$1-C236_$1 \\sim
C35D_$1-C236_$1 ~
 C30D_$1-C229_$1 \\sim C30C_$1-C229_$1 \\sim C31D_$1-C232_$1 \\sim
C31C_$1-C232_$1
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O1S \\sim C1S \\sim C4S \\sim C2S \\sim C3S \\sim O3S \\sim C9S \\sim C12S
\\sim C10S \\sim C11S \\sim O2S \\sim C5S \\sim C8S \\sim C6S \\sim C7S: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
O1 \\sim Mn1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim O2 \\sim O3
\\sim O4 \\sim O5 \\sim O7A \\sim Mn2A \\sim C6A \\sim C7A \\sim C8A \\sim C9A
\\sim C10A \\sim O6A \\sim O8A \\sim O9A \\sim O10A \\sim O6B \\sim Mn2B \\sim
C6B \\sim C7B \\sim C8B \\sim C9B \\sim C10B \\sim O7B \\sim O8B \\sim O9B
\\sim O10B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
O13 \\sim C132 \\sim C131 \\sim C130 \\sim C129 \\sim O14 \\sim C136 \\sim C133
\\sim C35A \\sim C35B \\sim C34A \\sim C34B \\sim O24 \\sim C233 \\sim C34C
\\sim C34D \\sim C35D \\sim C35C \\sim C236 \\sim C229 \\sim C30D \\sim C30C
\\sim C31C \\sim C31D \\sim C232: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 O1S, C1S, C4S, C2S, C3S, O3S, C9S, C12S, C10S, C11S, O2S, C5S, C8S, C6S, C7S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6B, Mn2B, C6B, C7B, C8B, C9B, C10B, O7B, O8B, O9B, O10B, O9A, Mn2A, C6A, C7A,
  C8A, C9A, C10A, O6A, O7A, O8A, O10A, O5, Mn1, C1, C2, C3, C4, C5, O1, O2, O3,
 O4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, C132, C131, C130, C129, O14, C133, C34A, C34B, C35B, C35A, C136, O24,
 C233, C34D, C34C, C35D, C35C, C236, O23, C229, C30D, C30C, C31C, C31D, C232
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{Mn1, O1, O2, O3, O4, O5, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
{Mn2B, O6B, O7B, O8B, O9B, O10B, C6B, C7B, C8B, C9B, C10B} sigma for 1-2: 0.02,
1-3: 0.04
as
{Mn2A, O6A, O7A, O8A, O9A, O10A, C6A, C7A, C8A, C9A, C10A}
{Mn1, O1, O2, O3, O4, O5, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as
{Mn2B, O6B, O7B, O8B, O9B, O10B, C6B, C7B, C8B, C9B, C10B}
{O13, C129, C130, C131, C132} sigma for 1-2: 0.02, 1-3: 0.04
{O1S, C4S, C3S, C2S, C1S} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1S, C1S, C2S, C3S, C4S}
{O13, C129, C130, C131, C132} sigma for 1-2: 0.02, 1-3: 0.04
{O2S, C8S, C7S, C6S, C5S} sigma for 1-2: 0.02, 1-3: 0.04
as
{O2S, C5S, C6S, C7S, C8S}
{O13, C129, C130, C131, C132} sigma for 1-2: 0.02, 1-3: 0.04
as
{O3S, C9S, C12S, C10S, C11S}
7. Others
 Sof(Mn2B)=Sof(O6B)=Sof(O7B)=Sof(O8B)=Sof(O9B)=Sof(O10B)=Sof(C6B)=Sof(C7B)=
 Sof(C8B)=Sof(C9B)=Sof(C10B)=1-FVAR(1)
 Sof(Mn2A)=Sof(O6A)=Sof(O7A)=Sof(O8A)=Sof(O9A)=Sof(O10A)=Sof(C6A)=Sof(C7A)=
 Sof(C8A)=Sof(C9A)=Sof(C10A)=FVAR(1)
 Sof(H13I)=Sof(H13J)=Sof(C34B)=Sof(H34G)=Sof(H34H)=Sof(C35B)=Sof(H35G)=
 Sof(H35H)=Sof(H13M)=Sof(H13N)=1-FVAR(2)
 Sof(H13G)=Sof(H13H)=Sof(C34A)=Sof(H34E)=Sof(H34F)=Sof(C35A)=Sof(H35E)=
 Sof(H35F)=Sof(H13K)=Sof(H13L)=FVAR(2)
 Sof(H22U)=Sof(H22V)=Sof(C30D)=Sof(H30C)=Sof(H30D)=Sof(C31D)=Sof(H31C)=
 Sof(H31D)=Sof(H23C)=Sof(H23D)=1-FVAR(3)
 Sof(H22S)=Sof(H22T)=Sof(C30C)=Sof(H30A)=Sof(H30B)=Sof(C31C)=Sof(H31A)=
 Sof(H31B)=Sof(H23A)=Sof(H23B)=FVAR(3)
 Sof(H23G)=Sof(H23H)=Sof(C34D)=Sof(H34C)=Sof(H34D)=Sof(C35D)=Sof(H35C)=
 Sof(H35D)=Sof(H23K)=Sof(H23L)=1-FVAR(4)
 Sof(H23E)=Sof(H23F)=Sof(C34C)=Sof(H34A)=Sof(H34B)=Sof(C35C)=Sof(H35A)=
 Sof(H35B)=Sof(H23I)=Sof(H23J)=FVAR(4)
8.a Ternary CH refined with riding coordinates:
 C108(H108), C113(H113), C208(H208), C213(H213)
8.b Secondary CH2 refined with riding coordinates:
 C109(H10A,H10B), C110(H11A,H11B), C111(H11C,H11D), C112(H11E,H11F), C129(H12S,
 H12T), C130(H13A,H13B), C131(H13C,H13D), C132(H13E,H13F), C133(H13G,H13H),
 C133(H13I,H13J), C34A(H34E,H34F), C35A(H35E,H35F), C34B(H34G,H34H), C35B(H35G,
 H35H), C136(H13K,H13L), C136(H13M,H13N), C209(H20A,H20B), C210(H21A,H21B),
 C211(H21C,H21D), C212(H21E,H21F), C229(H22S,H22T), C229(H22U,H22V), C30C(H30A,
 H30B), C31C(H31A,H31B), C30D(H30C,H30D), C31D(H31C,H31D), C232(H23A,H23B),
 C232(H23C,H23D), C233(H23E,H23F), C233(H23G,H23H), C34C(H34A,H34B), C35C(H35A,
 H35B), C34D(H34C,H34D), C35D(H35C,H35D), C236(H23I,H23J), C236(H23K,H23L),
 C1S(H1SA,H1SB), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C5S(H5SA,H5SB),
  C6S(H6SA,H6SB), C7S(H7SA,H7SB), C8S(H8SA,H8SB), C9S(H9SA,H9SB), C12S(H12U,
 H12V), C10S(H10C,H10D), C11S(H11G,H11H)
8.c Aromatic/amide H refined with riding coordinates:
 C103(H103), C105(H105), C107(H107), C114(H114), C116(H116), C118(H118),
 C203(H203), C205(H205), C207(H207), C214(H214), C216(H216), C218(H218)
8.d Idealised Me refined as rotating group:
 C122(H12A,H12B,H12C), C123(H12D,H12E,H12F), C124(H12G,H12H,H12I), C126(H12J,
 H12K,H12L), C127(H12M,H12N,H12O), C128(H12P,H12Q,H12R), C222(H22A,H22B,H22C),
 C223(H22D,H22E,H22F), C224(H22G,H22H,H22I), C226(H22J,H22K,H22L), C227(H22M,
 H22N,H22O), C228(H22P,H22Q,H22R)
;
_shelx_res_checksum              52906
_shelx_hkl_checksum              42927
_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 1.085
_oxdiff_exptl_absorpt_empirical_full_min 0.927