Enantioconvergent Copper Catalysis: In Situ Generation of the Chiral Phosphorus Ylide and Its Wittig Reactions.
Zhang, Kai; Lu, Liang-Qiu; Yao, Sheng; Chen, Jia-Rong; Shi, De-Qing; Xiao, Wen-Jing; Journal of the American Chemical Society 139 (2017) 12847–12854; doi:10.1021/jacs.7b08207

data_4131659
_publ_section_title
;
 Enantioconvergent Copper Catalysis: In Situ Generation of the Chiral
 Phosphorus Ylide and Its Wittig Reactions.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12847
_journal_page_last               12854
_journal_paper_doi               10.1021/jacs.7b08207
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C26 H30 Cu2 N6 O8), 4(B F4), 0.5(C Cl2)'
_chemical_formula_sum            'C52.5 H60 B4 Cl Cu4 F16 N12 O16'
_chemical_formula_weight         1751.97
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-04-28
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.541(2)
_cell_length_b                   28.224(3)
_cell_length_c                   11.1173(11)
_cell_measurement_reflns_used    8653
_cell_measurement_temperature    296.15(10)
_cell_measurement_theta_max      19.37
_cell_measurement_theta_min      2.31
_cell_volume                     7072.8(12)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_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, 2015)'
_diffrn_ambient_temperature      296.15(10)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0677
_diffrn_reflns_av_unetI/netI     0.0720
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            55224
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.333
_diffrn_reflns_theta_min         1.443
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.337
_exptl_absorpt_correction_T_max  0.7444
_exptl_absorpt_correction_T_min  0.5980
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1001 before and 0.0649 after correction.
The Ratio of minimum to maximum transmission is 0.8033.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.645
_exptl_crystal_description       block
_exptl_crystal_F_000             3536
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.948
_refine_diff_density_min         -0.565
_refine_diff_density_rms         0.105
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     907
_refine_ls_number_reflns         14363
_refine_ls_number_restraints     833
_refine_ls_restrained_S_all      34.130
_refine_ls_R_factor_all          0.1374
_refine_ls_R_factor_gt           0.0816
_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^)+(0.1661P)^2^+1.7528P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2244
_refine_ls_wR_factor_ref         0.2671
_reflns_Friedel_coverage         0.819
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                8347
_reflns_number_total             14363
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b08207_si_002.cif
_cod_data_source_block           t
_cod_original_cell_volume        7072.9(12)
_cod_original_formula_sum        'C52.50 H60 B4 Cl Cu4 F16 N12 O16'
_cod_database_code               4131659
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.99(3) 0.01(3)
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 O(H) groups
3. Shared sites
{C53, B4B}
4. Restrained distances
 H2-O2 = H2-O6 = H6A-O16_$5
 1.92 with sigma of 0.02
 H12_$1-O9_$2
 2.3 with sigma of 0.02
 F13-F15 = F13-F16 = F15-F16 = F14-F16 = F13-F14 = F15-F14 = F14B_$3-F15B_$3 =
 F16B_$3-F13B_$3
 2.3 with sigma of 0.02
 C18-C15
 1.48 with sigma of 0.02
 C17-C14
 1.5 with sigma of 0.02
 H16_$6-O14_$7
 2 with sigma of 0.02
 O10-C30 = O17-C30 = C43-O14 = O4-C13
 1.4 with sigma of 0.02
 H4-H8A
 2.2 with sigma of 0.04
 C22-C21 \\sim C21-C20 \\sim C20-C19 \\sim C19-C18
 with sigma of 0.01
 F9-F10 \\sim F9-F11 \\sim F9-F12 \\sim F10-F11 \\sim F10-F12 \\sim F11-F12
\\sim F9B-F10B \\sim F9B-F11B
 \\sim F9B-F12B \\sim F10B-F11B \\sim F10B-F12B \\sim F11B-F12B
 with sigma of 0.01
 F15-B4 \\sim F16-B4 \\sim F13-B4 \\sim F14-B4
 with sigma of 0.01
 F15-F16 \\sim F13-F16 \\sim F13-F15 \\sim F16-F14 \\sim F14-F15
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4 \\sim
F1B-F2B \\sim F1B-F3B \\sim F1B-F4B ~
 F2B-F3B \\sim F2B-F4B \\sim F3B-F4B
 with sigma of 0.02
 Cl2-B4B \\sim Cl1-C53
 with sigma of 0.01
 F3-B1 \\sim F2B-B1 \\sim F1B-B1 \\sim F4-B1 \\sim F1-B1 \\sim F2-B1 \\sim
F4B-B1 \\sim F3B-B1 \\sim F16B-B4B
 \\sim F14B-B4B \\sim F15B-B4B \\sim F11_$4-B3_$4 \\sim F10_$4-B3_$4 \\sim
F12B_$4-B3_$4 \\sim F9B_$4-
 B3_$4 \\sim F11B_$4-B3_$4 \\sim F9_$4-B3_$4 \\sim F10B_$4-B3_$4 \\sim
F12_$4-B3_$4 \\sim F5-B2 ~
 F5B-B2 \\sim F6B-B2 \\sim F6-B2 \\sim F7B-B2 \\sim F8B-B2 \\sim F8-B2 \\sim
F7-B2 \\sim F13-B4 \\sim F16-B4 ~
 F15-B4 \\sim F14-B4 \\sim F13B-B4B
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
O7 \\sim C25: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
Uanis(C22) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(N6) \\sim Ueq: with sigma of
0.007 and sigma for terminal atoms of 0.014
Uanis(C46) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(O15) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(O6) \\sim Ueq, Uanis(O14) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq,
Uanis(C18) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C30) \\sim Ueq,
Uanis(O5) \\sim Ueq, Uanis(O10) \\sim Ueq, Uanis(O7) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uiso(F13B) = Uiso(Cl1)
Uiso(F1) = Uiso(F1B)
Uiso(F2) = Uiso(F3B)
Uiso(F4B) = Uiso(F3)
6. Others
 Fixed Sof: H30A(0.5) H30B(0.5) H30C(0.5) H30D(0.5) O10(0.5) H10(0.5) F9(0.5)
 F9B(0.5) F10(0.5) F10B(0.5) F11(0.5) F11B(0.5) F12(0.5) F12B(0.5) F5(0.5)
 F5B(0.5) F6(0.5) F6B(0.5) F7(0.5) F7B(0.5) F8(0.5) F8B(0.5) F1(0.5) F1B(0.5)
 F2(0.5) F2B(0.5) F3(0.5) F4(0.5) F4B(0.5) B4(0.5) F13(0.5) F14(0.5) F15(0.5)
 F16(0.5) B4B(0.5) C53(0.5) Cl1(0.5) Cl2(0.5) F13B(0.5) F14B(0.5) F15B(0.5)
 F16B(0.5) F3B(0.5) O17(0.5) H17(0.5)
 Fixed Uiso: F9(0.18) F9B(0.18) F10(0.18) F10B(0.18) F11(0.18) F11B(0.18)
 F12(0.18) F12B(0.18) F2B(0.16) F4(0.16) B4(0.18) F13(0.18) F14(0.18) F15(0.18)
 F16(0.18) B4B(0.18) C53(0.18)
7.a Riding coordinates:
 O2(H2), O6(H6A), O10(H10), O12(H12), O16(H16), O17(H17)
7.b Ternary CH refined with riding coordinates:
 C1(H1), C11(H11), C14(H14), C24(H24), C27(H27), C37(H37), C40(H40), C50(H50)
7.c Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C12(H12A,H12B), C13(H13A,H13B), C16(H16A,H16B),
 C17(H17A,H17B), C25(H25A,H25B), C26(H26A,H26B), C29(H29A,H29B), C30(H30A,H30B),
  C30(H30C,H30D), C38(H38A,H38B), C39(H39A,H39B), C42(H42A,H42B), C43(H43A,
 H43B), C51(H51A,H51B), C52(H52A,H52B)
7.d Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C19(H19), C20(H20), C21(H21), C32(H32), C33(H33),
 C34(H34), C45(H45), C46(H46), C47(H47)
7.e Idealised tetrahedral OH refined as rotating group:
 O4(H4), O8(H8A), O14(H14A)
;
_shelx_res_checksum              5012
_shelx_hkl_checksum              58028
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'