Stereoselective synthesis of highly substituted cyclohexanes by a rhodium-carbene initiated domino sequence.
Parr, Brendan T.; Davies, Huw M. L.; Organic letters 17 (2015) 794–797; doi:10.1021/ol503508k

data_1518713
_publ_section_title
;
 Stereoselective synthesis of highly substituted cyclohexanes by a
 rhodium-carbene initiated domino sequence.
;
_journal_issue                   4
_journal_name_full               'Organic letters'
_journal_page_first              794
_journal_page_last               797
_journal_paper_doi               10.1021/ol503508k
_journal_volume                  17
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H27 F3 O3'
_chemical_formula_sum            'C23 H27 F3 O3'
_chemical_formula_weight         408.44
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-14
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.20970(10)
_cell_length_b                   14.9142(2)
_cell_length_c                   23.1930(3)
_cell_measurement_reflns_used    9831
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      68.238
_cell_measurement_theta_min      3.523
_cell_volume                     2147.97(5)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'APEX2 v2011.2-4 (Bruker, 2011)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0211
_diffrn_reflns_av_unetI/netI     0.0215
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            18263
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.706
_diffrn_reflns_theta_min         3.523
_diffrn_source                   'sealed tube'
_diffrn_source_current           35.0
_diffrn_source_power             1.4
_diffrn_source_voltage           40.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.836
_exptl_absorpt_correction_T_max  0.9517
_exptl_absorpt_correction_T_min  0.8673
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0427 before and 0.0353 after correction.
The Ratio of minimum to maximum transmission is 0.9113.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by slow evaporation'
_exptl_crystal_size_max          0.515
_exptl_crystal_size_mid          0.461
_exptl_crystal_size_min          0.34
_refine_diff_density_max         0.432
_refine_diff_density_min         -0.294
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 1593 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.07(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         3920
_refine_ls_number_restraints     223
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0407
_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^)+(0.0626P)^2^+0.5850P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1058
_refine_ls_wR_factor_ref         0.1067
_reflns_Friedel_coverage         0.710
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                3835
_reflns_number_total             3920
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol503508k_si_003.cif
_cod_data_source_block           bp_16_041a
_cod_depositor_comments
'Adding full bibliography for 1518712--1518713.cif.'
_cod_database_code               1518713
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.764
_shelx_estimated_absorpt_t_min   0.673
_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. Restrained distances
 C23B-C20 \\sim C23A-C20 \\sim C23C-C20
 with sigma of 0.003
 F3C-C23C \\sim F2C-C23C \\sim F1C-C23C
 with sigma of 0.003
 F3C-F1C \\sim F3C-F2C \\sim F2C-F1C
 with sigma of 0.003
 F2B-C23B \\sim F1B-C23B \\sim F3B-C23B
 with sigma of 0.003
3. Rigid bond restraints
 C23B, F1B, F2B, F3B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F3C, C23C
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C23C, F1C, F2C, F3C
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C23C, F1C, F2C, F3C
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
F1B \\sim F2B \\sim F3B: within 2.5A with sigma of 0.004 and sigma for terminal
atoms of 0.008
F3A \\sim F2A \\sim F1A: within 2.5A with sigma of 0.005 and sigma for terminal
atoms of 0.01
F1C \\sim F3C \\sim F2C: within 2.5A with sigma of 0.004 and sigma for terminal
atoms of 0.008
F2A \\sim F2C: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.004
Uanis(F3B) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.01
Uanis(F1A) = Uanis(F1B)
Uanis(C23A) = Uanis(C23B) = Uanis(C23C)
Uanis(F1C) = Uanis(F1B)
Uanis(F3B) = Uanis(F2A)
5. Rigid body (RIGU) restrains
 C23A, F1A, F2A, F3A, C23B, F1B, F2B, F3B, C23C, F1C, F2C, F3C
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C17, C12
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C20, C19, C18, C21, C22, C17, C12, C13, C10
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Same fragment restrains
{C23C, F1C, F2C, F3C}
as
{C23A, F1A, F2A, F3A}
{C23C, F1C, F2C, F3C}
as
{C23B, F1B, F2B, F3B}
7. Others
 1*[Sof(C23A)+Sof(F1A)+Sof(F2A)+Sof(F3A)]+1*[Sof(C23B)+Sof(F1B)+Sof(F2B)+
 Sof(F3B)]+1*[Sof(C23C)+Sof(F1C)+Sof(F2C)+Sof(F3C)]=1 with esd of 0.0001
 Sof(C23A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(1)
 Sof(C23B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=FVAR(2)
 Sof(C23C)=Sof(F1C)=Sof(F2C)=Sof(F3C)=FVAR(3)
8.a Ternary CH refined with riding coordinates:
 C4(H4), C8(H8), C10(H10), C12(H12)
8.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C9(H9A,H9B), C13(H13A,H13B)
8.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C18(H18), C19(H19), C21(H21), C22(H22)
8.d X=CH2 refined with riding coordinates:
 C2(H2A,H2B)
8.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C11(H11A,H11B,H11C), C16(H16A,H16B,H16C)
8.f Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              57610
_shelx_hkl_checksum              51511
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id BP-16-041A
_olex2_submission_special_instructions 'No special instructions were received'