Beyond FLP additions: FLP deprotonation and C-O bond cleavage of aliphatic, aryl and ester derived olefins
Goraya, Armaan; Ajithkumar, V. S.; Ruhlandt, Karin; Stephan, Douglas W.; McCahill, Jenny SJ; Bedi, Vaibhav; Chemical Communications  (2026) –; doi:10.1039/D6CC00412A

data_7135374
_publ_section_title
;
 Beyond FLP additions: FLP deprotonation and C-O bond cleavage of
 aliphatic, aryl and ester derived olefins.
;
_journal_issue                   19
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5531
_journal_page_last               5535
_journal_paper_doi               10.1039/d6cc00412a
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C H Cl3, C34.75 H35 B F15 O2 P, 0.9[CHCl3]'
_chemical_formula_sum            'C36.65 H36.9 B Cl5.7 F15 O2 P'
_chemical_formula_weight         1038.254
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_audit_creation_date             2026-01-10
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-01-11 deposited with the CCDC.	2026-02-13 downloaded from the CCDC.
;
_cell_angle_alpha                99.437(3)
_cell_angle_beta                 91.072(3)
_cell_angle_gamma                118.514(2)
_cell_formula_units_Z            2
_cell_length_a                   13.1112(15)
_cell_length_b                   13.1605(15)
_cell_length_c                   15.0066(17)
_cell_measurement_reflns_used    9953
_cell_measurement_temperature    150.01
_cell_measurement_theta_max      23.59
_cell_measurement_theta_min      2.47
_cell_volume                     2230.4(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150.01
_diffrn_measured_fraction_theta_full 0.9589
_diffrn_measured_fraction_theta_max 0.9589
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0601
_diffrn_reflns_av_unetI/netI     0.0876
_diffrn_reflns_Laue_measured_fraction_full 0.9589
_diffrn_reflns_Laue_measured_fraction_max 0.9589
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            54574
_diffrn_reflns_point_group_measured_fraction_full 0.9589
_diffrn_reflns_point_group_measured_fraction_max 0.9589
_diffrn_reflns_theta_full        24.9999
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         2.77
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.498
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6717
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0809 before and 0.0592 after correction.
The Ratio of minimum to maximum transmission is 0.9006.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.546
_exptl_crystal_description       block
_exptl_crystal_F_000             1052.153
_refine_diff_density_max         1.3865
_refine_diff_density_min         -1.0528
_refine_diff_density_rms         0.1105
_refine_ls_d_res_high            0.8409
_refine_ls_d_res_low             7.3553
_refine_ls_extinction_coef       0.024(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0340
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    82
_refine_ls_number_parameters     587
_refine_ls_number_reflns         7542
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0340
_refine_ls_R_factor_all          0.1110
_refine_ls_R_factor_gt           0.0804
_refine_ls_shift/su_max          0.0013
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1836P)^2^+0.2284P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2459
_refine_ls_wR_factor_ref         0.2647
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -15
_reflns_limit_k_max              15
_reflns_limit_k_min              -15
_reflns_limit_l_max              17
_reflns_limit_l_min              0
_reflns_number_gt                4887
_reflns_number_total             7542
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d6cc00412a2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7135371--7135375.cif.'
_cod_original_formula_sum        'C36.65 H36.9 B1 Cl5.7 F15 O2 P1'
_cod_database_code               7135374
_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 C(H,H,H,H,H,H) groups
2. Others
 Fixed Sof: H7a(0.75) H7b(0.75) H7c(0.75) H49a(0.25) H49b(0.25) H2a(0.75)
 H2b(0.75) H2c(0.75) H3a(0.75) H3b(0.75) H3c(0.75) H4a(0.75) H4b(0.75)
 H4c(0.75) H5a(0.75) H5b(0.75) H5c(0.75) H6a(0.75) H6b(0.75) H6c(0.75)
 H8a(0.75) H8b(0.75) H8c(0.75) H10a(0.75) H10b(0.75) H10c(0.75) H17a(0.5)
 H17b(0.5) H17c(0.5) H17a(0.5) H17b(0.5) H17c(0.5) H39a(0.25) H39b(0.25)
 H39c(0.25) C22(0.25) H38a(0.25) H38b(0.25) H38c(0.25) H9a(0.75) H9b(0.75)
 H9c(0.75) H42a(0.25) H42b(0.25) H42c(0.25) H45a(0.25) H45b(0.25) H45c(0.25)
 C23(0.25) H16a(0.25) H16b(0.25) H16c(0.25) C7(0.25) H48a(0.25) H48b(0.25)
 H48c(0.25) C6(0.25) H47a(0.25) H47b(0.25) H47c(0.25) C14(0.25) H46a(0.25)
 H46b(0.25) H46c(0.25) H49a(0.25) H49b(0.25) H49c(0.25) H2(0.5) C6(0.25)
 H6a(0.25) H6b(0.25) H6c(0.25) C9(0.75) C3(0.75) H3a(0.75) H3b(0.75) H3c(0.75)
 C11(0.75) H11a(0.75) H11b(0.75) H11c(0.75) H4aa(0.75) H4ab(0.75) H4ac(0.75)
 H4bd(0.25) H4be(0.25) H4bf(0.25) C10(0.75) H10a(0.75) H10b(0.75) H10c(0.75)
 C12(0.75) H12a(0.75) H12b(0.75) H12c(0.75) H12d(0.25) H12e(0.25) H12f(0.25)
 H2aa(0.75) H2ab(0.75) H2ac(0.75) H2bd(0.25) H2be(0.25) H2bf(0.25) H19a(0.75)
 H19b(0.75) H19c(0.75) H19d(0.25) H19e(0.25) H19f(0.25) C17(0.75) C1(0.75)
 C13(0.25) C5(0.25) C21(0.25) C8(0.25) H8a(0.25) H8b(0.25) H8c(0.25) C18(0.75)
 H18a(0.75) H18b(0.75) H18c(0.75) C16(0.25) H16a(0.25) H16b(0.25) H16c(0.25)
 C15(0.25) H15a(0.25) H15b(0.25) H15c(0.25) C6(0.25) H6b(0.25) H6c(0.25)
 H6a(0.25)
 Fixed U23: H46b(-4.978497)
 Fixed U33: H46b(7.348379)
3.a Ternary CH refined with riding coordinates:
 C47(H47)
3.b Secondary CH2 refined with riding coordinates:
 C24(H24a,H24b), C27(H27a,H27b)
3.c Me refined with riding coordinates:
 C3(H3a,H3b,H3c), C11(H11a,H11b,H11c), C4(H4aa,H4ab,H4ac), C4(H4bd,H4be,H4bf),
 C10(H10a,H10b,H10c), C12(H12a,H12b,H12c), C12(H12d,H12e,H12f), C20(H20a,H20b,
 H20c), C2(H2aa,H2ab,H2ac), C2(H2bd,H2be,H2bf), C19(H19a,H19b,H19c), C19(H19d,
 H19e,H19f), C28(H28a,H28b,H28c), C8(H8a,H8b,H8c), C18(H18a,H18b,H18c),
 C16(H16a,H16b,H16c), C15(H15a,H15b,H15c), C6(H6b,H6c,H6a)
3.d Aromatic/amide H refined with riding coordinates:
 C25(H25)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 104 electrons were 
found in a volume of 290\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.9[CHCl3] per Asymmetric Unit 
which account for 104 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'