Supporting Information. C2-Alkylation and Alkenylation of Indoles Catalyzed by a Low-Valent Cobalt Complex in the absence of Reductant

Supporting Information C2-Alkylation and Alkenylation of Indoles Catalyzed by a Low-Valent Cobalt Complex in the absence of Reductant Brendan J. Fallon, [a] Etienne Derat, [a] Muriel Amatore, [a] Corinne Aubert, [a] Fabrice Chemla, [a] Franck Ferreira, [a] Alejandro Pérez-Luna, [a] and Marc Petit* [a] Institut Parisien de Chimie Moléculaire, UMR 8232, Université Pierre et Marie Curie-Paris 6, Case 229, 4 Place Jussieu, 75252 Paris, France List of the Contents of the Supporting Information I. General information. S2 II. Deuterium and mechanistic studies...s3 III. DFT calculations.. S6 IV. Preparation of starting materials. S18 V. Characterization of new compounds.s22 VI. 1 H NMR Spectra of products S45 VII. References. S86 S1

I. General information: Commercial reagents were purified prior to use following the guidelines of Perrin and Armarego. 1 Toluene was purified by mean of distillation under dry nitrogen atmosphere on benzophenone/sodium ketyl and degassed by sparging argon. Organic solutions were concentrated under reduced pressure on a Büchi rotary evaporatory. Chromatographic purifications of products were accomplished using force-flow chromatography on Davisil (LC60A) SI 60 Å (40 63 μm) silica gel according to the method of Still. 2 Thin layer chromatography (TLC) was performed on Merck 60 F254 silica gel plates. TLC visualization was performed by fluorescence quenching (λ = 254 nm), dipping in KMnO 4 or paraanisaldehyde stains. Filtrations through Celite were performed using Hyflo Super Cel from Fluka. 1 H NMR spectra were recorded on a Brucker 400 AVANCE or 300 AVANCE (400 and 300 MHz respectively) and are referenced relative to residual CDCl 3 protons signals at δ 7.26 ppm. 13 C NMR spectra were recorded on a Brucker 400 AVANCE or 300 AVANCE (100 and 75 MHz respectively) and are referenced relative to CDCl 3 at δ 77.00 ppm. 19 F NMR spectra were recorded on a Brucker 400 AVANCE (376 MHz) and are referenced relative to CFCl 3 at δ 0.00 ppm. Data are reported as follows: chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, qt = quintuplet, m = multiplet, bs = broad signal), coupling constant (Hz) and integration. IR spectra were recorded on a Bruker Tensor 27 (ATR diamond) and are reported in terms of frequency of absorption (cm-1). High-resolution Mass spectra were obtained from the Laboratoire Structure et Fonction de Molécules Bioactives (Université Pierre et Marie Curie, Paris 6). S2

III. Deuterium and mechanistic experiments: 1 H NMR Spectra of deuteriated and non deuteriated indoles 98% deuterium incorporation S3

(a) Deuterium labeling experiment (see scheme 2a in article) Sm. >98% D 0.78H 0.78H 2.47H 0.7H 0.78H 0.86H 22% 2.47 66% 2.47 Recovery of the starting material showed a significant decrease of the deuterium content (0.04 H to 0.7H). Deuterium was included into all TWO alkene position alpha and beta (0.78H). The desired product was isolated with a marginal (<20% ) incorporation of deuterium in the α position. Consistent with this observation the methyl group was substantially deuteriated >50% 63% 2.47 S4

(b) Hydrogen/Deuterium transfer study (see scheme 2b in article) Deuterium labeled indole 1a-d was reacted with diphenylacetylene 2a in the presence of 50 mol% HCo(PMe 3 ) 4. No hydrogen incorporation was observed in the final product. This result suggested that C-H bond activation and functionalization proceeded in a concerted manner for the hydro-complex. This hypothesis was further substantiated by DFT calculations. S5

(c) Competition experiment (see scheme 3a in article) S6

II. DFT Calculations XYZ coordinates CH activation with diphenylacetylene Reagent Co 27.0-0.43050739-1.06316304 0.03477350 N 7.0-1.74982035 0.06607950-0.88688481 C 6.0-2.90954971 0.52436191-0.51064640 C 6.0-3.56713676 0.18440720 0.72082728 C 6.0-3.16466618-0.73964149 1.68446171 C 6.0-1.17674661 0.52816761-2.10211468 C 6.0-0.57751411-0.40000680-2.96770215 C 6.0-1.13193059 1.89500189-2.44120646 C 6.0-0.51538187 2.31405044-3.61578274 C 6.0 0.07561160 1.37912846-4.48548269 C 6.0 0.03960150 0.01511340-4.15165758 O 8.0 0.65355867 1.88710332-5.60361958 C 6.0 1.27025890 1.01134145-6.52017260 H 1.0-2.28855395-1.38734400 1.68647647 H 1.0-0.61814040-1.46156156-2.70870662 H 1.0-1.56433439 2.63405085-1.76074278 H 1.0-0.46581230 3.37299252-3.88341475 H 1.0 0.48362130-0.73827410-4.80446720 H 1.0 0.54841971 0.28396419-6.94367647 H 1.0 2.10941100 0.45450759-6.05660057 H 1.0 1.66406918 1.64016938-7.33446360 P 15.0 0.55180049 0.45107639 1.30222154 C 6.0 2.33587074 0.88802040 1.04976904 C 6.0-0.20976560 2.14150643 1.33103979 C 6.0 0.52340341 0.01719590 3.10058570 H 1.0 2.68399167 1.64115655 1.78098035 H 1.0 2.46749830 1.28541100 0.02779770 H 1.0 2.95179486-0.02254700 1.14285111 H 1.0-0.11012090 2.59823656 0.33045560 H 1.0 0.26406890 2.80249405 2.08007717 H 1.0-1.28649569 2.04407477 1.55580962 H 1.0 1.01517475 0.78974700 3.72000265 H 1.0 1.02615309-0.95431072 3.24484229 S7

H 1.0-0.52796400-0.08995340 3.42109466 C 6.0-0.85512441-2.88244700-0.17431040 C 6.0 0.11441560-2.75851226 0.70622140 C 6.0-1.70346844-3.85216761-0.84697241 C 6.0 0.86974692-3.49693203 1.70451200 C 6.0-1.41974914-5.23646736-0.82654870 C 6.0-2.25162601-6.14653969-1.48127627 C 6.0-3.39046931-5.69839191-2.16506529 C 6.0-3.68552756-4.32975245-2.19457030 C 6.0-2.84757495-3.41740513-1.54889631 C 6.0 2.19629884-3.14315009 2.03046632 C 6.0 0.28511679-4.57528830 2.40888238 C 6.0 2.91122055-3.83728147 3.00999403 C 6.0 2.31291604-4.89635658 3.70392060 C 6.0 0.99429250-5.25937366 3.39812064 H 1.0-0.53119272-5.58579445-0.29178190 H 1.0-2.01339746-7.21563816-1.45797038 H 1.0-4.04361439-6.41445971-2.67487097 H 1.0-4.57273579-3.97182465-2.72811699 H 1.0-3.06284237-2.34502697-1.57049096 H 1.0 2.66075659-2.31330323 1.48984492 H 1.0-0.74328530-4.86281204 2.16910338 H 1.0 3.94307303-3.54800367 3.23744941 H 1.0 2.86990285-5.43598843 4.47674847 H 1.0 0.51661009-6.08715248 3.93376231 N 7.0-4.07351828-0.78877568 2.70526409 C 6.0-5.10096312 0.10620690 2.44329071 C 6.0-4.82106066 0.73867428 1.20005906 C 6.0-6.24289227 0.40343869 3.19754744 C 6.0-7.12066936 1.35903609 2.68569469 C 6.0-6.86264610 1.99946821 1.45437145 C 6.0-5.72293949 1.69861126 0.70924962 C 6.0-3.99437571-1.64856315 3.86677861 H 1.0-5.53623247 2.20435023-0.24321650 H 1.0-7.57166576 2.74480748 1.08027005 H 1.0-8.02422047 1.61577225 3.24777174 H 1.0-6.44093466-0.09498210 4.15061045 H 1.0-4.86967707-2.32191968 3.91435552 H 1.0-3.08032632-2.25924587 3.80240464 H 1.0-3.96028781-1.05008638 4.79565620 H 1.0-3.44697118 1.21486843-1.17948341 Transition state S8

Co 27.0 0.68895888 0.36415109 0.51567990 N 7.0-1.40281188-0.72720528 0.41212341 C 6.0-1.77015984-0.98581129 1.63717484 C 6.0-0.90189862-0.62169349 2.70382214 C 6.0 0.32752150-0.00308970 2.37684608 C 6.0-2.21546340-0.98335481-0.69523108 C 6.0-1.60702574-1.37111986-1.90187061 C 6.0-3.61921835-0.81614941-0.68985552 C 6.0-4.37313366-1.04376018-1.83717394 C 6.0-3.75332212-1.44366896-3.03435731 C 6.0-2.35797429-1.60574031-3.05785799 O 8.0-4.57594347-1.63479578-4.10176229 C 6.0-4.01979971-2.02500153-5.33458471 H 1.0 1.35410833-0.86405110 1.04385614 H 1.0-0.52100128-1.49050665-1.91923976 H 1.0-4.11918926-0.47518149 0.22193611 H 1.0-5.45780087-0.90411282-1.83856869 H 1.0-1.84029007-1.91092312-3.96937156 H 1.0-3.49982643-3.00211740-5.26339531 H 1.0-3.30550599-1.27020454-5.72340202 H 1.0-4.86015368-2.11858845-6.04121113 P 15.0-0.32008311 2.37512231 0.64006311 C 6.0-1.84562135 2.60358810-0.36661071 C 6.0-0.89656150 2.88327837 2.31855512 C 6.0 0.71040529 3.82501745 0.14660300 H 1.0-2.27894664 3.60782671-0.20792720 H 1.0-2.58114290 1.83136046-0.08795140 H 1.0-1.60213065 2.47465992-1.43276656 H 1.0-1.59232199 2.12056637 2.70689988 H 1.0-1.39511526 3.86906099 2.29310918 H 1.0-0.03327700 2.92442870 3.00425410 H 1.0 0.15781809 4.77264977 0.28016949 H 1.0 1.01185119 3.72151852-0.90924633 H 1.0 1.62403953 3.84844637 0.76637369 C 6.0 1.90830207-0.41864580-0.80851948 C 6.0 1.37018585 0.62160438-1.33515918 C 6.0 2.79205966-1.54606128-1.06135237 C 6.0 1.27839041 1.48630357-2.49556422 C 6.0 3.52202868-1.57658255-2.27081323 C 6.0 4.37106848-2.64395142-2.56331730 C 6.0 4.50990534-3.70405531-1.65690005 C 6.0 3.79090691-3.68583679-0.45659381 C 6.0 2.94103503-2.61693311-0.16154380 C 6.0 0.09374670 1.56117022-3.25811648 C 6.0 2.37922359 2.27950239-2.88557649 S9

C 6.0 0.01588170 2.40225315-4.37095118 C 6.0 1.10986459 3.19401431-4.74136782 C 6.0 2.29186773 3.12612176-3.99383092 H 1.0 3.41018271-0.74864542-2.97758389 H 1.0 4.92918444-2.65115404-3.50546503 H 1.0 5.17581511-4.54188156-1.88766694 H 1.0 3.89087582-4.51154804 0.25537089 H 1.0 2.37401628-2.60353589 0.77421921 H 1.0-0.75802761 0.93582588-2.97778964 H 1.0 3.30276728 2.22919965-2.30088806 H 1.0-0.91085410 2.43965840-4.95317745 H 1.0 1.04297149 3.85762525-5.60929346 H 1.0 3.15567255 3.73675919-4.27737331 N 7.0 0.99016720 0.24474400 3.54822612 C 6.0 0.22723749-0.17629570 4.64264917 C 6.0-0.98426688-0.73703182 4.14257669 C 6.0 0.50992131-0.09923460 6.00761938 C 6.0-0.44695500-0.59901643 6.89915371 C 6.0-1.65006721-1.15783668 6.42723608 C 6.0-1.92677462-1.23096871 5.05849218 C 6.0 2.29202700 0.86045587 3.65264440 H 1.0-2.86650610-1.66911733 4.70717096 H 1.0-2.38087320-1.54221702 7.14632559 H 1.0-0.25588530-0.55458927 7.97616386 H 1.0 1.44597471 0.33529359 6.37060022 H 1.0 3.00546646 0.19372690 4.17208672 H 1.0 2.66161394 1.05553961 2.63346767 H 1.0 2.23970771 1.81508863 4.21045113 H 1.0-2.72766137-1.49373829 1.85173285 Product Co 27.0 0.49056050 0.41661689 0.63541931 N 7.0-1.42685401-0.64168519 0.50573182 C 6.0-1.90377235-0.83428079 1.71087086 C 6.0-1.10888100-0.45467609 2.82495785 C 6.0 0.14318590 0.13483830 2.53509617 C 6.0-2.19932461-0.91899228-0.63271618 C 6.0-1.58517003-1.49261999-1.75789857 C 6.0-3.57489967-0.60937738-0.71999592 C 6.0-4.29964018-0.87635279-1.87782848 C 6.0-3.67440987-1.45813489-2.99444699 C 6.0-2.30627990-1.76824224-2.92364979 O 8.0-4.46462965-1.67681408-4.08015394 S10

C 6.0-3.88070512-2.15738225-5.26778173 H 1.0 1.68815374-0.97396982 0.45376709 H 1.0-0.52002859-1.72853839-1.70795214 H 1.0-4.07387638-0.12751471 0.12644340 H 1.0-5.36147547-0.62530190-1.95145965 H 1.0-1.78562057-2.22061753-3.76989269 H 1.0-3.46787000-3.17921138-5.14277458 H 1.0-3.07211971-1.48941326-5.62932205 H 1.0-4.68421841-2.18793654-6.02128267 P 15.0-0.20298889 2.48080778 0.63622522 C 6.0-1.71512628 2.72727394-0.38428071 C 6.0-0.69454819 3.21189952 2.25832748 C 6.0 0.95071870 3.75473380-0.03372960 H 1.0-2.07256627 3.77141571-0.32851329 H 1.0-2.50271654 2.04194427-0.03037040 H 1.0-1.48499346 2.47084045-1.43097198 H 1.0-1.45758426 2.56615400 2.72505283 H 1.0-1.09130847 4.23652220 2.13908291 H 1.0 0.18131430 3.23299623 2.92870784 H 1.0 0.49444851 4.76093149-0.00825660 H 1.0 1.21505213 3.49488473-1.07259285 H 1.0 1.87708044 3.76085806 0.56699389 C 6.0 1.93493176-0.69157052-0.63280272 C 6.0 1.24095726 0.34605911-1.12611055 C 6.0 2.88448119-1.67933345-1.16729033 C 6.0 1.30397987 1.06028259-2.39615440 C 6.0 3.28228307-1.68784654-2.52172756 C 6.0 4.17553663-2.64984441-2.99490619 C 6.0 4.69352055-3.62688875-2.13439369 C 6.0 4.30294037-3.63449097-0.79085708 C 6.0 3.40947866-2.67260861-0.31529149 C 6.0 0.15764000 1.21348667-3.20439434 C 6.0 2.49726200 1.69294918-2.81081009 C 6.0 0.20871730 1.95465779-4.38772917 C 6.0 1.39580154 2.58447766-4.78108740 C 6.0 2.53939247 2.45011330-3.98387384 H 1.0 2.88006973-0.93905210-3.20719790 H 1.0 4.46931267-2.63884377-4.04986668 H 1.0 5.39384031-4.37962008-2.51053691 H 1.0 4.69487095-4.39590359-0.10837790 H 1.0 3.10416698-2.68954110 0.73713249 H 1.0-0.77267408 0.72766721-2.90018249 H 1.0 3.39365911 1.58789098-2.19188857 H 1.0-0.69201529 2.04857349-5.00370598 H 1.0 1.43023372 3.17495465-5.70227528 S11

H 1.0 3.47461104 2.93705750-4.28034925 N 7.0 0.73324031 0.42777160 3.73420978 C 6.0-0.08853590 0.05066680 4.80251026 C 6.0-1.27740908-0.52025110 4.25925112 C 6.0 0.12433940 0.16924050 6.17766953 C 6.0-0.88316733-0.29051760 7.03385210 C 6.0-2.06413054-0.85922998 6.51901293 C 6.0-2.26946855-0.97795850 5.14098072 C 6.0 2.02508187 1.05275714 3.89366031 H 1.0-3.19274926-1.42343438 4.75658369 H 1.0-2.83414626-1.21423614 7.21186495 H 1.0-0.74863738-0.21040060 8.11739826 H 1.0 1.04454112 0.60761452 6.57511091 H 1.0 2.73534083 0.38219360 4.41368961 H 1.0 2.41972589 1.28392613 2.89159346 H 1.0 1.94405985 1.98916066 4.47789717 H 1.0-2.89572501-1.29544330 1.85511446 CH activation with styrene Reagent Co 27.0-0.32944560-1.20587468-0.17270251 N 7.0-1.68083775-0.15348800-1.07243717 C 6.0-2.84837961 0.23338120-0.61421889 C 6.0-3.35095739-0.14598051 0.67396468 C 6.0-2.78233528-1.03727639 1.58398914 C 6.0-1.19168460 0.42914751-2.27140641 C 6.0-0.55607331-0.37512329-3.22821379 C 6.0-1.26379633 1.81782186-2.50870061 C 6.0-0.72582281 2.37274313-3.66533732 C 6.0-0.09753380 1.55794811-4.62427711 C 6.0-0.01730020 0.17459010-4.39586830 O 8.0 0.39973301 2.19387412-5.71668720 C 6.0 1.05261564 1.44219315-6.71364689 H 1.0-1.92288995-1.70140195 1.48565316 H 1.0-0.50205928-1.45014393-3.05003023 H 1.0-1.72241426 2.46864820-1.75928187 H 1.0-0.76713169 3.44994521-3.84853125 H 1.0 0.45828861-0.49012050-5.11940622 H 1.0 0.37707800 0.69275922-7.17397738 H 1.0 1.94729805 0.92066622-6.31682777 H 1.0 1.37008440 2.15961361-7.48708439 P 15.0 0.51052719 0.30981341 1.23922098 S12

C 6.0 2.34267569 0.56216192 1.17766559 C 6.0-0.10616170 2.04553342 1.05568886 C 6.0 0.23710570 0.02126540 3.04727387 H 1.0 2.67494726 1.34428346 1.88502395 H 1.0 2.63648963 0.85112458 0.15318459 H 1.0 2.84279680-0.38939220 1.42541897 H 1.0 0.14510991 2.41297126 0.04530880 H 1.0 0.32550281 2.72669029 1.81203926 H 1.0-1.20648575 2.04115438 1.15312481 H 1.0 0.76855600 0.77412510 3.65774059 H 1.0 0.59202039-0.98832822 3.31568313 H 1.0-0.84380949 0.08296850 3.25960970 C 6.0-0.23378900-3.08157158-0.81014812 C 6.0 0.80637121-2.84655094 0.16175839 C 6.0 0.77588832-3.31002235 1.56000662 C 6.0 1.91824961-3.16184521 2.38281488 C 6.0-0.36687729-3.88734651 2.16302466 C 6.0 1.91240275-3.53000736 3.72890615 C 6.0 0.76199120-4.07947540 4.31094122 C 6.0-0.37098029-4.26512146 3.50902987 H 1.0 2.83196259-2.74563694 1.94348526 H 1.0-1.26392519-4.05900097 1.56065965 H 1.0 2.81800461-3.39362335 4.33034754 H 1.0 0.75523692-4.37545013 5.36451721 H 1.0-1.27068877-4.72376299 3.93509102 N 7.0-3.51130748-1.06028628 2.74999905 C 6.0-4.58235312-0.19098739 2.62730551 C 6.0-4.52268887 0.40092149 1.33484983 C 6.0-5.59088516 0.12253420 3.54883337 C 6.0-6.55523491 1.05092204 3.15676594 C 6.0-6.51339102 1.65135014 1.87936842 C 6.0-5.50610399 1.33573294 0.96784002 C 6.0-3.21666336-1.85516238 3.92282891 H 1.0-5.48503304 1.80828977-0.01908300 H 1.0-7.28592348 2.37563372 1.60260117 H 1.0-7.35831690 1.31759262 3.85113525 H 1.0-5.62280321-0.34357250 4.53753710 H 1.0-4.01404047-2.59910846 4.10757351 H 1.0-2.26224852-2.38254714 3.77371073 H 1.0-3.12810493-1.20802796 4.81437683 H 1.0-3.46812868 0.90875590-1.22143328 H 1.0 0.08141670-3.22470975-1.85637605 H 1.0-1.08900690-3.72683311-0.55466968 H 1.0 1.83037424-2.70503402-0.21999530 S13

Transition state Co 27.0 0.67349100-0.30276969 0.37903970 N 7.0-1.44786739-0.45858559-0.54665279 C 6.0-2.30885363-0.35370111 0.43323240 C 6.0-1.82919800-0.25335759 1.76648045 C 6.0-0.42624220-0.17101160 1.96210146 C 6.0-1.83483160-0.35743499-1.88642979 C 6.0-1.12603772-1.08224344-2.86017108 C 6.0-2.86125445 0.50663710-2.33374667 C 6.0-3.17076635 0.61653519-3.68602443 C 6.0-2.46361089-0.12771089-4.64632940 C 6.0-1.43187666-0.98096842-4.22020245 O 8.0-2.83653569 0.05411610-5.94186831 C 6.0-2.15136385-0.63860881-6.95780993 H 1.0 0.34621480-1.51278222 1.30990505 H 1.0-0.31789130-1.73854876-2.53060818 H 1.0-3.40070701 1.12462652-1.60973644 H 1.0-3.95664549 1.29358399-4.03270197 H 1.0-0.85647321-1.57075810-4.93641424 H 1.0-2.24715781-1.73800766-6.84616756 H 1.0-1.07384288-0.37599280-6.98221540 H 1.0-2.61461258-0.33504680-7.91033363 P 15.0 1.03285158 1.68498731-0.45918670 C 6.0 1.27099836 1.75274062-2.28717756 C 6.0-0.31989771 2.90884495-0.19391450 C 6.0 2.53460622 2.55517292 0.16906179 H 1.0 1.42230546 2.78819656-2.64363265 H 1.0 0.38628429 1.31454146-2.78009486 H 1.0 2.15268278 1.14280236-2.54770184 H 1.0-1.24047685 2.51150775-0.65559310 H 1.0-0.08216170 3.89308167-0.63690603 H 1.0-0.50168413 3.01780152 0.88888699 H 1.0 2.66599727 3.54029322-0.31481749 H 1.0 3.42034221 1.92535114-0.02659690 H 1.0 2.44591212 2.69467258 1.26058674 C 6.0 1.13199234-2.32418537 0.47480139 C 6.0 1.88023841-1.61661732-0.57619709 C 6.0 3.24811792-1.12031281-0.36016840 C 6.0 4.04241085-0.71500432-1.45904636 C 6.0 3.79790735-0.92900121 0.93109828 C 6.0 5.29513311-0.12826671-1.27884674 C 6.0 5.81149769 0.07126150 0.00936600 C 6.0 5.05291033-0.34150970 1.11044705 H 1.0 3.65538740-0.86462963-2.47309852 S14

H 1.0 3.22754622-1.23599601 1.81326616 H 1.0 5.87943649 0.17515101-2.15448594 H 1.0 6.79375029 0.53264040 0.15033939 H 1.0 5.44171715-0.20434050 2.12539291 N 7.0-0.21784990-0.06150210 3.31540155 C 6.0-1.43136609-0.06253960 4.00840282 C 6.0-2.48256588-0.18101691 3.05360508 C 6.0-1.67499483 0.04164600 5.38012075 C 6.0-3.00773668 0.02502840 5.80693913 C 6.0-4.06158495-0.09397470 4.88024521 C 6.0-3.81069660-0.19781549 3.50890017 C 6.0 1.07252383 0.09266480 3.94621539 H 1.0-4.64048386-0.29064870 2.80070591 H 1.0-5.09492016-0.10561250 5.24196386 H 1.0-3.23265409 0.10416900 6.87539482 H 1.0-0.85472000 0.13181420 6.09830904 H 1.0 1.31101441-0.77022821 4.59704113 H 1.0 1.83616042 0.17387460 3.15625238 H 1.0 1.10158908 1.00972772 4.56409073 H 1.0-3.39500427-0.33518529 0.23395750 H 1.0 0.36489001-3.02327108 0.11105670 H 1.0 1.72048354-2.76720595 1.29568875 H 1.0 1.63714099-1.86397755-1.61595678 Product Co 27.0 0.32818481 0.34248430 0.15410520 N 7.0-1.49462998-0.90100503 0.39422381 C 6.0-1.73605669-1.03350079 1.67805815 C 6.0-0.81804758-0.49364191 2.61349368 C 6.0 0.26913741 0.25015649 2.09147334 C 6.0-2.48651433-1.19479537-0.55245429 C 6.0-2.14155912-1.80895364-1.76813555 C 6.0-3.84066725-0.83092350-0.36873469 C 6.0-4.79624939-1.08233774-1.34891129 C 6.0-4.43575525-1.70509362-2.55608749 C 6.0-3.09397173-2.06828332-2.75823545 O 8.0-5.43766642-1.90019774-3.45565009 C 6.0-5.14355803-2.51217985-4.68866158 H 1.0 1.37589669-1.06872106 0.11397880 H 1.0-1.10341096-2.10293913-1.93160295 H 1.0-4.13652325-0.31231239 0.54834980 H 1.0-5.84091663-0.79046768-1.20930648 H 1.0-2.77492571-2.55492091-3.68183804 S15

H 1.0-4.74854517-3.54029918-4.55632448 H 1.0-4.41177702-1.92288554-5.27852821 H 1.0-6.09245777-2.56383657-5.24629831 P 15.0-0.77553552 2.22771311-0.00647640 C 6.0-1.86565912 2.36167955-1.48533535 C 6.0-1.94813359 2.57775354 1.37275934 C 6.0 0.22577751 3.77447414-0.08022810 H 1.0-2.43748164 3.30749583-1.48463309 H 1.0-2.56281447 1.50595903-1.49124563 H 1.0-1.24369597 2.31092525-2.39332676 H 1.0-2.64249349 1.72747815 1.47533882 H 1.0-2.52061677 3.50493407 1.18934059 H 1.0-1.38594174 2.66436481 2.31746387 H 1.0-0.42158550 4.66627455-0.16442131 H 1.0 0.90823752 3.73031783-0.94556242 H 1.0 0.83486068 3.85346246 0.83722472 C 6.0 1.47758114-1.10478449-1.05514073 C 6.0 0.86055791 0.07119570-1.75252211 C 6.0 1.72227895 1.20629692-2.12204814 C 6.0 1.40388012 2.04121494-3.21802521 C 6.0 2.84814382 1.57332206-1.34338403 C 6.0 2.14600539 3.18879294-3.50304961 C 6.0 3.24359035 3.54393816-2.70730448 C 6.0 3.59049201 2.72180605-1.62874413 H 1.0 0.55643028 1.77282083-3.85829639 H 1.0 3.13601303 0.95478421-0.48589030 H 1.0 1.86881649 3.81192088-4.36047935 H 1.0 3.82557201 4.44342136-2.93074870 H 1.0 4.44963741 2.97779202-0.99909258 N 7.0 0.96780479 0.73945129 3.16093636 C 6.0 0.37945861 0.34250119 4.36867380 C 6.0-0.76583099-0.44765720 4.05824566 C 6.0 0.76231188 0.62221831 5.68196774 C 6.0-0.02522640 0.09924160 6.71503019 C 6.0-1.16163838-0.68163830 6.43086290 C 6.0-1.53740442-0.96035480 5.11271667 C 6.0 2.14731550 1.56910515 3.07306123 H 1.0-2.42176199-1.57255280 4.90814018 H 1.0-1.75982165-1.07866633 7.25764084 H 1.0 0.24773830 0.30027941 7.75595903 H 1.0 1.64606631 1.22917974 5.89960766 H 1.0 3.02444243 1.07131994 3.52854991 H 1.0 2.35422635 1.76104355 2.00793791 H 1.0 1.99264419 2.53540277 3.59008479 H 1.0-2.65756011-1.53425729 2.02252722 S16

H 1.0 0.99946511-2.06323910-1.30702412 H 1.0 2.57221246-1.19289088-1.17405891 H 1.0 0.08638400-0.16673081-2.49203753 Energetic data diphenylacetylene E (u.a.) ZPC (u.a.) S DE (kcal/mol) DH (kcal/mol) DG (kcal/mol) Reagent -3223.131768 0.6011422 1.02431 0.00 0.00 0.00 TS -3223.112064 0.595739 0.97544 12.36 8.97 12.46 Product -3223.137614 0.6012092 0.99585-3.67-3.63-1.60 Styrene E (u.a.) ZPC (u.a.) S DE (kcal/mol) DH (kcal/mol) DG (kcal/mol) Reagent -2993.608204 0.5422316 0.87555 0.00 0.00 0.00 TS -2993.589622 0.5383477 0.89237 11.66 9.22 8.02 Product -2993.615607 0.5428832 0.88294-4.65-4.24-4.76 S17

Iv. Preparation of starting materials: General procedure (A) for the preparation of indole precursors: Indole precursors were prepared through N-alkylation of indole-3-carboxaldehyde with methyl iodide, benzyl bromide or alkyl bromide with NaH as base in DMF. The corresponding carbonyl compounds were condensed with para-anisidine in toluene with MS 4Å to afford the corresponding indole substrates which were purified by precipitation from pentane/et 2 O. The 1 H NMR spectrum of all compounds showed good agreement with the literature data. (E)-N-(4-Methoxyphenyl)-1-(1-methyl-1H-indol-3-yl)methanimine (1a) 3 (E)-N-(4-Methoxyphenyl)-1-(1-methyl-1H-indol-3-yl-2-d)methanimine (1a-d) 3 (E)-1-(1-Benzyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1b) 3 (E)-1-(5-Methoxy-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1d) 3 (E)-1-(5-Fluoro-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1h) 3 (E)-1-(1-(But-3-en-1-yl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (4a) 4 (E)-1-(1-((E)-Hex-3-en-1-yl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (4c) 4 (E)-N-(4-Methoxyphenyl)-1-(1-(2-methylbut-3-en-1-yl)-1H-indol-3-yl)methanimine (4d) 4 (E)-1-(1,7-Dimethyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1c) Pale yellow solid (53 %). mp 142-144 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.64 (s, 1H), 8.35 (ddd, J = 7.9, 1.4, 0.7 Hz, 1H), 7.42 (s, 1H), 7.27 7.23 (m, 2H), 7.16 (dd, J = 7.9, 7.2 Hz, 1H), 7.03 (dt, J = 7.1, 1.1 Hz, 1H), 6.98 6.93 (m, 2H), 4.11 (s, 3H), 3.86 (s, 3H), 2.79 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.3, 152.6, 146.7, 135.5, 135.2, 127.2, 125.9, 123.1, 121.8 (2C), 121.6, 121.3, 120.0, 114.3 (2C), 55.5, 37.3, 19.6. IR (thin film): max = 2989, 1619, 1545, 1242, 744 cm -1. HRMS (ESI): calculated for C 18 H 19 N 2 O [M+ H] + : 279.1492; found 279.1499. S18

(E)-1-(5-(Benzyloxy)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1e) White solid (44 %). mp 157-159 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.63 (s, 1H), 8.16 (d, J = 2.5 Hz, 1H), 7.55 (m, 2H), 7.48 7.40 (m, 3H), 7.39 7.33 (m, 1H), 7.30 7.23 (m, 3H), 7.08 (dd, J = 8.9, 2.5 Hz, 1H), 7.00 6.94 (m, 2H), 5.21 (s, 2H), 3.87 (s, 3H), 3.82 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 154.8, 152.7, 146.7, 137.5, 134.3, 133.1, 128.5 (2C), 127.8 (2C), 127.7, 126.5, 121.8 (2C), 114.7, 114.3 (2C), 114.0, 110.2, 105.4, 70.7, 55.5, 33.4. IR (thin film): max = 2978, 1598, 1467, 1376, 1250, 1052, 896 cm -1. HRMS (ESI): calculated for C 24 H 23 N 2 O 2 [M+ H] + : 371.1754; found 371.1748. Methyl (E)-3-(((4-methoxyphenyl)imino)methyl)-1-methyl-1H-indole-6-carboxylate (1f) white solid (44 %). mp 175-177 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.67 (s, 1H), 8.50 (dd, J = 8.4, 0.7 Hz, 1H), 8.15 (dd, J = 1.5, 0.7 Hz, 1H), 7.99 (dd, J = 8.4, 1.4 Hz, 1H), 7.70 (s, 1H), 7.29 7.23 (m, 2H), 7.00 6.91 (m, 2H), 3.99 (s, 3H), 3.94 (s, 3H), 3.86 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 167.8, 157.6, 151.9, 148.8, 137.3, 136.2, 131.1 129.5, 124.8, 122.4, 121.8 (2C), 121.7, 114.3 (2C), 111.8, 55.5, 52.1, 33.5. IR (thin film): max = 2946, 1701, 1594, 1500, 1266, 891, 879 cm -1. HRMS (ESI): calculated for C 19 H 19 N 2 O 3 [M+ H] + : 323.1390; found 323.1397. (E)-1-(5-Isocyano-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1g) yellow solid (73 %). mp 190-192 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.96 (dd, J = 1.6, 0.7 Hz, 1H), 8.63 (s, 1H), 7.63 7.51 (m, 2H), 7.41 (dd, J = 8.6, 0.7 Hz, 1H), 7.31 7.20 (m, 2H), 7.05 6.92 (m, 2H), 3.90 (s, 3H), 3.87 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.8, 151.1, 145.6, 139.2, 135.4, 128.4, 126.2, 125.6, 121.9 (2C), 120.4, 115.9, 114.4 (2C), 110.3, 104.6, 55.5, 33.5. IR (thin film): max = 3289, 2938, 2217, 1623, 1539, 1388, 1121, 834 cm -1. HRMS (ESI): calculated for C 18 H 16 N 3 O [M+ H] + : 290.1288; found 290.1285. S19

(E)-1-(6-Chloro-1-methyl-1H-indol-3-yl)-N-(4- methoxyphenyl)methanimine (1i) Yellow solid (60 %). mp 125-127 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.60 (s, 1H), 8.45 (dd, J = 8.5, 0.5 Hz, 1H), 7.45 (s, 1H), 7.35 (dd, J = 1.8, 0.6 Hz, 1H), 7.29 7.27 (m, 1H), 7.26 7.22 (m, 2H), 6.98 6.93 (m, 2H), 3.86 (s, 3H), 3.80 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.52, 152.13, 146.28, 138.28, 134.39, 129.18, 124.45, 123.41, 122.05, 121.87 (2C), 115.30, 114.34 (2C), 109.60, 55.52, 33.31. IR (thin film): max = 2966, 1987, 1564, 1480, 1104, 811 cm -1. HRMS (ESI): calculated for C 17 H 16 N 2 OCl [M+ H] + : 299.0946; found 299.0957 (E)-1-(1-(But-3-en-1-yl)-1H-indol-3-yl)-N-(4-methoxyphenyl)ethan-1-imine (4b) Orange solid (53 %). mp 69-71 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.36 8.22 (m, 1H), 7.64 (s, 1H), 7.33 7.12 (m, 3H), 6.75 6.62 (m, 2H), 6.61 6.47 (m, 2H), 5.70 (m, 1H), 5.11 4.91 (m, 2H), 4.21 4.04 (m, 2H), 3.66 (s, 3H), 2.54 (m, 2H), 2.44 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 161.8, 155.4, 145.4, 137.0, 134.2, 131.0, 123.5, 122.7, 121.3 (2C), 117.8, 117.1, 116.6, 114.1 (2C), 109.4, 60.4, 55.5, 46.2, 34.3, 17.9. IR (thin film): max = 2936, 1636, 1526, 1465, 1340, 823 cm -1. HRMS (ESI): calculated for C 21 H 23 N 2 O [M+ H] + : 319.1805; found 319.1802 S20

(E)-1-(1-(But-3-en-1-yl)-5-methoxy-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (4e) Yellow solid (41 %). mp 72-74 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.54 (s, 1H), 7.93 (d, J = 2.6 Hz, 1H), 7.42 (s, 1H), 7.24 7.07 (m, 3H), 6.89 6.81 (m, 3H), 5.70 (dd, J = 17.3, 10.0 Hz, 1H), 5.09 4.90 (m, 2H), 4.11 (t, J = 7.1 Hz, 2H), 3.84 (s, 3H), 3.76 (s, 3H), 2.53 (m, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 155.6, 152.8, 146.8, 134.0, 133.1, 132.1, 126.7, 121.8 (2C), 118.0, 116.4, 114.3 (2C), 113.4, 110.4, 103.8, 55.8, 55.5, 46.5, 34.2. IR (thin film): max = 3011, 2937, 1616, 1499, 1288, 1104, 745 cm -1. HRMS (ESI): calculated for C 21 H 23 N 2 O 2 [M+ H] + : 335.1754; found 335.1751. Methyl (E)-1-(but-3-en-1-yl)-3-(((4-methoxyphenyl)imino)methyl)-1H-indole-6-carboxylate (4f) Yellow solid (41 %). mp 83-85 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.58 (s, 1H), 8.41 (dd, J = 8.4, 0.7 Hz, 1H), 8.07 (dd, J = 1.5, 0.7 Hz, 1H), 7.95 (dd, J = 8.4, 1.4 Hz, 1H), 7.62 (s, 1H), 7.17 7.13 (m, 2H), 6.89 6.84 (m, 2H), 5.80 5.64 (m, 1H), 5.06 4.96 (m, 2H), 4.23 (t, J = 7.1 Hz, 2H), 3.90 (s, 3H), 3.77 (s, 3H), 2.63 2.52 (m, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 167.8, 162.0, 152.0, 136.5 (2C), 135.1, 133.6, 129.7, 125.1, 124.8, 122.4, 121.8 (2C), 118.3, 115.3, 114.3 (2C), 111.9, 55.5, 52.1, 46.5, 34.3. IR (thin film): max = 2947, 1706, 1616, 1535, 1462, 1286, 878, 789 cm -1. HRMS (ESI): calculated for C 22 H 23 N 2 O 3 [M+ H] + : 363.1691; found 363.1703. Synthesis of catalysts: Co(PMe 3 ) 4 and HCo(PMe 3 ) 4 were synthesised according to literature methods and showed good agreement with the literature data. 5,6 Note care should be taken when handling these catalysts as they are combustible in air. S21

V. Characterization of new compounds. General procedure B: Cobalt catalysed hydroarylation of internal alkynes: To a sealed tube under argon were added Co(PMe 3 ) 4 (5 mol %), imine (0.5mmol) and alkyne (0.6 mmol). Degassed toluene (1 ml) was added and the resulting solution was heated at 170 C for 1 h in the microwave (absorption level normal). The reaction mixture was then filtered through a plug of celite washing with ethyl acetate (3 x 10 ml). The crude product was purified by silica chromatography to yield the desired product. (E)-1-(2-((Z)-1,2-Diphenylvinyl)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (3aa) 7 The general procedure (B) was applied to (E)-N-(4-methoxyphenyl)-1-(1- methyl-1h-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.) and diphenylacetylene (2a, 106.8 mg, 0.60 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 80/20) afforded the title compound (3aa) as a yellow solid (218.7 mg, 99 %). mp; 79-82 o C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.74 8.69 (m, 1H), 8.38 (s, 1H), 7.51 (s, 1H), 7.41 7.34 (m, 8H), 7.20 7.16 (m, 3H), 7.09 7.04 (m, 2H), 6.94 6.89 (m, 2H), 6.81 6.83 (m, 2H), 3.79 (s, 3H), 3.49 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.1, 153.7, 146.8, 143.7, 140.9, 137.9, 135.9, 134.4, 129.7, 128.9 (2C), 128.8 (2C), 128.7 (2C), 128.2, 128.2, 126.4 (2C), 125.7, 123.3, 123.1, 121.9, 121.8 (2C), 114.1 (2C), 112.8, 109.5, 55.4, 30.4. IR (thin film): max = 3055, 2934, 1615, 1500, 1243, 1076, 777, 695 cm -1. HRMS (ESI): calculated for C 31 H 26 N 2 O [M+ H] + : 443.2118; found 443.2118. (E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-((Z)-1-phenyl-2-(trimethylsilyl)vinyl)-1H-indol-3- yl)methanimine (3ab) The general procedure (B) was applied to (E)-N-(4-methoxyphenyl)-1-(1- methyl-1h-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.) and trimethyl(phenylethynyl)silane (2b, 104.1 mg, 0.60 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 80/20) afforded the title compound (3ab) as a yellow oil (202.1 mg, 92 %) as a mixture of stereoisomers 90/10 S22

anti/syn as determined by 1 H NMR. The characteristic peaks for the minor isomer as determined by 1 H NMR are as follows: δ 6.23 (s, 1H), 3.83 (s, 3H), 3.41 (s, 3H). Major isomer: 1 H NMR (400 MHz, CDCl 3 ) δ 8.76 (ddd, J = 6.6, 3.0, 1.8 Hz, 1H), 8.51 (s, 1H), 7.38 7.27 (m, 8H), 7.21 7.17 (m, 2H), 6.99 (s, 1H), 6.91 6.87 (m, 2H), 3.81 (s, 3H), 3.49 (s, 3H), -0.10 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.0, 154.9, 147.7, 146.4, 145.3, 141.0, 138.5, 138.2, 129.6 (2C), 129.4, 127.0 (2C), 126.3, 124.1, 124.1, 122.8 (2C), 122.7, 115.2 (2C), 115.1, 110.1, 56.3, 31.2, 0.0 (3C). IR (thin film): max = 2951, 1615, 1574, 1499, 1464, 1242, 909 cm -1. HRMS (ESI): calculated for C 31 H 26 N 2 O [M+ H] + : 439.2200; found 439.2196. (Z)-1-Methyl-2-(1-phenylhex-1-en-1-yl)-1H-indole-3-carbaldehyde (3ac) A modified version of procedure (B) was applied to (E)-N-(4-methoxyphenyl)- 1-(1-methyl-1H-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.) and hex-1-yn-1-ylbenzene (2c, 95 mg, 0.60 mmol, 1.2 eq.). The resulting mixture was quenched with 3M HCl (1.0 ml). The resulting mixture was then stirred at room temperature for 1 h, and then extracted with ethyl acetate (3 x 10 ml). The combined organic layer was dried over MgSO 4 and concentrated under reduced pressure. Silica gel chromatography (eluent pentane/etoac 80/20) afforded the title compound (3ac) as a yellow oil (218.7 mg, 65 %) as a mixture of stereoisomers 88/12 anti/syn as determined by 1 H NMR. The characteristic peaks for the minor isomer as determined by 1 H NMR are as follows: δ 9.89 (s, 1H), 6.06 (t, J = 7.5 Hz, 1H). Major Isomer: 1 H NMR (400 MHz, CDCl 3 ) δ 9.77 (s, 1H), 8.40 8.32 (m, 1H), 7.35 7.11 (m, 6H), 7.05 6.98 (m, 1H), 6.78 6.73 (m, 1H), 6.64 (t, J = 7.5 Hz, 1H), 3.42 (d, J = 1.2 Hz, 3H), 2.02 (m, J = 7.4 Hz, 2H), 1.48 1.14 (m, 4H), 0.77 (t, J = 7.3 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 186.1, 149.3, 138.9, 138.0, 129.1, 128.8, 128.6, 128.0 (2C), 127.9, 125.9 (2C), 125.1, 123.6, 123.1, 122.2, 115.8, 109.7, 31.3, 30.3, 22.3, 13.8. IR (thin film): max = 2929, 1652, 1464, 1382, 1046, 751 cm -1. HRMS (ESI): calculated for C 22 H 23 NNaO [M+ H] + : 340.1672; found 340.1660. S23

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-((Z)-1-(pyridin-3-yl)-2-(trimethylsilyl)vinyl)-1Hindol-3-yl)methanimine (3ad) The general procedure (B) was applied to (E)-N-(4-methoxyphenyl)-1- (1-methyl-1H-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.) and 3-((trimethylsilyl)ethynyl)pyridine (2d, 105.1 mg, 0.60 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 75/25) afforded the title compound (3ad) as a yellow oil (217.3 mg, 99 %). 1 H NMR (400 MHz, CDCl 3 ) δ 8.77 8.71 (m, 1H), 8.70 8.66 (m, 1H), 8.52 (dd, J = 4.8, 1.6 Hz, 1H), 8.49 (s, 1H), 7.48 (ddd, J = 8.0, 2.4, 1.6 Hz, 1H), 7.40 7.32 (m, 3H), 7.25 7.14 (m, 3H), 7.07 (s, 1H), 6.92 6.85 (m, 2H), 3.80 (s, 3H), 3.50 (s, 3H), -0.09 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.3, 154.3, 150.4, 148.3, 147.6, 144.8, 142.6, 141.3, 138.3, 136.7, 134.3, 126.4, 124.5, 124.4, 124.2, 123.0, 122.8 (2C), 115.6, 115.2 (2C), 110.3, 56.4, 31.3, -0.0 (3C). IR (thin film): max = 2951, 1615, 1498, 1464, 1437, 1408, 1241, 1034, 835, 748 cm -1. HRMS (ESI): calculated for C 27 H 30 N 3 OSi [M+ H] + : 440.2153; found 440.2143. (E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-((Z)-1-phenyl-2-(trimethylsilyl)vinyl)-1H-indol-3- yl)methanimine (3ae) The general procedure (B) was applied to (E)-N-(4-methoxyphenyl)-1-(1- methyl-1h-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.) and oct-4-yne (2e, 66.3 mg, 0.60 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 90/10) afforded the title compound (3ae) as a yellow oil (185.1 mg, 99 %) as a mixture of stereoisomers 79/21 anti/syn as determined by 1 H NMR. The characteristic peaks for the minor isomer as determined by 1 H NMR are as follows: δ 8.67 (s, 1H), 5.80 (t, J = 7.4 Hz, 1H). Major isomer: 1 H NMR (400 MHz, CDCl 3 ) δ 8.79 (m, 1H), 8.58 (s, 1H), 7.48 7.36 (m, 3H), 7.34 7.25 (m, 2H), 7.07 6.97 (m, 2H), 6.09 (m, 1H), 3.92 (s, 3H), 3.75 (d, J = 6.2 Hz, 3H), 2.58 2.34 (m, 2H), 1.96 (m, 1H), 1.70 1.33 (m, 4H), 1.12 (m, 1H), 1.02 (m, 3H), 0.92 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.1, 154.0, 147.3, 146.2, 137.6, 135.9, 130.1, S24

125.6, 122.7, 122.7, 121.8 (2C), 121.6, 114.3 (2C), 112.1, 109.2, 55.5, 41.0, 31.8, 30.3, 22.4, 21.5, 13.9, 13.8. IR (thin film): max = 2956, 2869, 1614, 1498, 1463, 1370, 1241, 1035, 747 cm -1. HRMS (ESI): calculated for C 25 H 31 N 2 O [M+ H] + : 375.2431; found 375.2420. (E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-((Z)-1-phenyl-2-(trimethylsilyl)vinyl)-1H-indol-3- yl)methanimine (3af) The general procedure (B) was applied to (E)-N-(4-methoxyphenyl)-1- (1-methyl-1H-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.) and dec-5-yne (2f, 83.1 mg, 0.60 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 90/10) afforded the title compound (3af) as a yellow oil (164.4 mg, 82 %) as a mixture of stereoisomers 78/22 anti/syn as determined by 1 H NMR. The characteristic peaks for the minor isomer as determined by 1 H NMR are as follows: δ 8.63 (s, 1H), 5.76 (s, 1H). Major isomer: 1 H NMR (400 MHz, CDCl 3 ) δ 8.75 (m, 1H), 8.55 (d, J = 0.8 Hz, 1H), 7.43 7.34 (m, 3H), 7.29 7.24 (m, 2H), 7.04 6.97 (m, 2H), 6.05 (m, 1H), 3.89 (s, 3H), 3.72 (d, J = 5.8 Hz, 3H), 2.58 2.30 (m, 2H), 2.04 1.86 (m, 2H), 1.68 1.19 (m, 7H), 1.06 (m, 1H), 0.97 0.90 (m, 3H), 0.90 0.82 (m, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.1, 154.0, 147.3, 146.2, 137.6, 136.0, 130.1, 125.6, 122.7, 122.6, 121.8 (2C), 121.6, 114.3 (2C), 112.1, 109.2, 55.5, 38.6, 31.5, 30.4, 30.3, 29.5, 22.5, 22.3, 13.9, 13.8. IR (thin film): max = 2926, 1614, 1498, 1463, 1436, 1240, 1103, 747 cm -1. HRMS (ESI): calculated for C 27 H 35 N 2 O [M+ H] + : 403.2744; found 403.2748. General procedure (C) : Cobalt catalysed intermolecular hydroarylation of alkenes: To a sealed tube under argon were added Co(PMe 3 ) 4 (10 mol %), imine (0.5mmol) and alkene (0.6-1.0 mmol). Degassed toluene (1 ml) was added and the resulting solution was heated at 170 C for 1 h in the microwave (absorption level normal). The reaction mixture was then filtered through a plug of celite washing with ethyl acetate (3 x 10 ml). The crude product was purified by silica chromatography to yield the desired product. S25

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)methanimine (3ag) The general procedure (C) was applied to (E)-N-(4-methoxyphenyl)-1- (1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 90/10) afforded the title compound (3ag) as a yellow foam (182 mg, 99 %). mp 59-61 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.79 (s, 1H), 8.70 8.64 (m, 1H), 7.39 7.29 (m, 8H), 7.20 7.15 (m, 2H), 6.95 6.91 (m, 2H), 5.15 (q, J = 7.4 Hz, 1H), 3.85 (s, 3H), 3.50 (s, 3H), 1.89 (d, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 δ 157.2, 153.0, 148.2, 147.1, 141.9, 137.6, 128.6 (2C), 127.1 (2C), 126.5, 125.9, 122.7, 122.2, 121.8 (2C), 121.6, 114.2 (2C), 111.8, 108.8, 55.5, 34.5, 30.9, 18.6. IR (thin film): max = 3053, 2940, 1613, 1498, 1242, 783 cm -1. HRMS (ESI): calculated for C 25 H 25 N 2 O [M+ H] + : 369.1973; found 369.1961 (E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-(p-tolyl)ethyl)-1Hindol-3-yl)methanimine (3ah) The general procedure (C) was applied to (E)-N-(4- methoxyphenyl)-1-(1-methyl-1h-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and 1-methyl-4-vinylbenzene (2h, 70 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography on silica (eluent pentane/etoac 90/10) afforded the title compound (3ah) as a yellow oil (182 mg, 99 %). 1 H NMR (400 MHz, CDCl 3 ) δ 8.77 (s, 1H), 8.69 8.64 (m, 1H), 7.32 7.27 (m, 3H), 7.20 7.12 (m, 6H), 6.95 6.89 (m, 2H), 5.10 (q, J = 8 Hz, 1H), 3.83 (s, 3H), 3.49 (s, 3H), 2.35 (d, J = 0.7 Hz, 3H), 1.85 (d, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 153.1, 148.5, 147.2, 138.9, 137.6, 136.1, 129.3 (2C), 127.0 (2C), 125.9, 122.6, 122.3, 121.8 (2C), 121.6, 114.2 (2C), 111.8, 108.8, 55.5, 34.2, 30.9, 20.9, 18.7. IR (thin film): max = 2936, 1612, 1574, 1497, 1240, 1061, 964, 777 cm -1. HRMS (ESI): calculated for C 26 H 26 N 2 O [M+ H] + : 383.2122; found 383.2118. S26

(E)-N-(4-Methoxyphenyl)-1-(2-(1-(3-methoxyphenyl)ethyl)-1- methyl-1h-indol-3-yl)methanimine (3ai) The general procedure (C) was applied to (E)-N-(4- methoxyphenyl)-1-(1-methyl-1h-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and 1-methoxy-3-vinylbenzene (2i, 68 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography on silica (eluent pentane/etoac 85/15) afforded the title compound (3ai) as a yellow oil (179.6 mg, 90 %). 1 H NMR (400 MHz, CDCl 3 ) δ 8.81 (s, 1H), 8.72 8.62 (m, 1H), 7.29 (dt, J = 16.3, 5.8 Hz, 4H), 7.20 (d, J = 8.4 Hz, 2H), 6.99 6.86 (m, 4H), 6.82 (d, J = 8.5 Hz, 1H), 5.13 (d, J = 7.4 Hz, 1H), 3.86 (s, 3H), 3.79 (s, 3H), 3.52 (s, 3H), 1.87 (d, J = 7.3 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.0, 157.2, 152.9, 148.0, 147.2, 143.7, 137.6, 129.7, 125.9, 122.7 (2C), 122.2, 121.8, 121.6, 119.6, 114.3 (2C), 113.5, 111.8, 111.3, 108.8, 55.5, 55.2, 34.5, 31.0, 18.6. IR (thin film): max = 2939, 1612, 1499, 1468, 1242, 1035, 912, 749 cm -1. HRMS (ESI): calculated for C 26 H 27 N 2 O 2 [M+ H] + : 399.2067; found 399.2055. (E)-N-(4-Methoxyphenyl)-1-(2-(1-(2-methoxyphenyl)ethyl)-1-methyl-1H-indol-3- yl)methanimine (3aj) The general procedure (C) was applied to (E)-N-(4-methoxyphenyl)-1-(1-methyl-1H-indol-3- yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and 1-methoxy-2-vinylbenzene (2j, 83 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography on silica (eluent pentane/etoac 90/10) afforded a mixture of the title compound (3aj) and the product of linear addition as a yellow foam (169 mg, 85 %). The branched/linear ratio was determined to be 76/24 by 1 H NMR. S27

Characteristic peaks for the linear product are 3.33 (t, J = 7.8 Hz, 2H) and 3.03 (t, J = 7.8 Hz, 2H). Note: NMR signals are only assigned to the major isomer. mp 68-79 C 1 H NMR (400 MHz, CDCl 3 ) δ 8.78 (s, 1H), 8.71 8.67 (m, 1H), 7.51 7.46 (m, 1H), 7.36 7.26 (m, 5H), 7.10 7.05 (m, 3H), 6.93 6.85 (m, 2H), 4.96 (q, J = 7.4 Hz, 1H), 3.85 (s, 3H), 3.78 (s, 3H), 3.68 (s, 3H), 1.84 (d, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 157.0, 154.0, 149.1, 147.3, 137.1, 130.8, 128.1, 127.2, 126.0, 122.8, 122.2, 121.9 (2C), 121.8, 121.4, 120.4, 114.1 (2C), 111.0, 110.8, 108.7, 55.4, 31.0, 30.1, 19.8. IR (thin film): max = 2936, 1592, 1497, 1242, 1033, 748 cm -1. HRMS (ESI): calculated for C 26 H 27 N 2 O 2 [M+ H] + : 399.2067; found 399.2069 (E)-1-(2-(1-(4-Fluorophenyl)ethyl)-1-methyl-1H-indol-3-yl)-N-(4- methoxyphenyl)methanimine (3ak) The general procedure (C) was applied to (E)-N-(4-methoxyphenyl)- 1-(1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and 1-fluoro-4-vinylbenzene (2k, 73 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography on silica (eluent pentane/etoac 90/10) afforded the title compound (3ak) as a yellow oil (162.6 mg, 84 %). 1 H NMR (400 MHz, CDCl 3 ) δ 8.67 (s, 1H), 8.58 8.48 (m, 1H), 3.75 3.72 (m, 3H), 7.24 7.13 (m, 5H), 7.09 7.05 (m, 2H), 6.96 6.90 (m, 2H), 6.85 6.81 (m, 2H), 5.06 (q, J = 7.9 Hz, 1H), 3.38 (s, 3H), 1.77 (d, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 161.5 (d, J = 245.5 Hz), 157.3, 152.7, 147.7, 147.1, 137.7 (d, J = 3.2 Hz), 137.6, 130.06 (d, J = 7.9 Hz), 128.64 (d, J = 8.0 Hz), 125.9, 122.8, 122.2, 121.8 (2C), 121.7, 115.6, 115.3, 114.3 (2C), 111.8, 108.8, 55.5, 33.9, 30.9, 18.8. 19 F NMR (376 MHz, CDCl 3 ) δ -116.2. IR (thin film): max = 2939, 1574, 1439, 1179, 1003, 831, 778 cm -1 HRMS (ESI): calculated for C 25 H 23 N 2 OF [M+ H] + : 387.1868; found 387.1867. S28

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-(naphthalen-2- yl)ethyl)-1h-indol-3-yl)methanimine (3al) The general procedure (C) was applied to (E)-N-(4- methoxyphenyl)-1-(1-methyl-1h-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and 2-vinylnaphthalene (2l, 93 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography on silica (eluent pentane/etoac 90/10) afforded the title compound (3al) as a yellow oil (136.0 mg, 65 %). 1 H NMR (400 MHz, CDCl 3 ) δ 8.81 (s, 1H), 8.69 8.63 (m, 1H), 7.85 7.79 (m, 3H), 7.77 (d, J = 8.6 Hz, 1H), 7.55 7.45 (m, 2H), 7.36 7.26 (m, 4H), 7.15 7.07 (m, 2H), 6.89 6.83 (m, 2H), 5.28 (q, J = 7.3 Hz, 1H), 3.81 (s, 3H), 3.48 (s, 3H), 1.98 (d, J = 7.3 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 153.0, 147.9, 147.1, 139.5, 137.7, 133.4, 132.1, 128.4, 127.8, 127.6, 126.3, 126.1, 125.9, 125.8, 124.8, 122.7, 122.2, 121.8 (2C), 121.7, 114.2 (2C), 111.9, 108.8, 55.5, 34.8, 30.9, 18.6. IR (thin film): max = 3003, 1677, 1468, 1106, 908, 730 cm -1 HRMS (ESI): calculated for C 29 H 26 N 2 O [M+ H] + : 418.2120; found 418.2118. (E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-phenylpropyl)-1H-indol-3-yl)methanimine (3am) The general procedure (C) was applied to (E)-N-(4- methoxyphenyl)-1-(1-methyl-1h-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and (E)-prop-1-en-1-ylbenzene (2m, 78 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 70/30) afforded the title compound (3am) as a yellow oil (105.3 mg, 55 %). 1 H NMR (400 MHz, CDCl 3 ) δ 8.85 (s, 1H), 8.73 8.67 (m, 1H), 7.38 7.29 (m, 8H), 7.23 7.16 (m, 2H), 6.99 6.91 (m, 2H), 4.87 (dd, J = 10.2, 5.9 Hz, 1H), 3.86 (s, 3H), 3.53 (s, 3H), 2.55 (m, 1H), 2.24 (m, 1H), 1.05 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 153.2, 147.2, 146.5, 141.4, 137.6, 128.6 (2C), 127.5 (2C), 126.6, 125.9, 122.6, 122.3, 121.8 (2C), 121.6, 114.3 (2C), S29

113.3, 108.8, 55.5, 42.2, 30.9, 25.6, 12.7. IR (thin film): max = 2962, 1613, 1240, 1150, 806 cm -1. HRMS (ESI): calculated for C 26 H 27 N 2 O [M+ H] + : 383.2118; found 383.2122. (E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-(pyridin-4-yl)ethyl)-1H-indol-3-yl)methanimine (3an) The general procedure (C) was applied to (E)-N-(4-methoxyphenyl)-1- (1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and 4-vinylpyridine (2n, 65 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 70/30) afforded the title compound (3an) as a yellow foam (182 mg, 99 %). mp 63-65 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.65 (s, 1H), 8.46 (m, 3H), 7.25 7.16 (m, 3H), 7.11 (dt, J = 4.6, 1.2 Hz, 2H), 7.07 7.00 (m, 2H), 6.85 6.76 (m, 2H), 5.18 5.09 (m, 1H), 3.71 (s, 3H), 3.36 (s, 3H), 1.76 (d, J = 7.3 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.4, 152.2, 151.3, 150.1 (2C), 146.8, 145.7, 137.5, 126.0, 123.0 (2C), 122.3 (2C), 121.8 (3C), 114.3 (2C), 112.1, 109.0, 55.5, 34.1, 31.1, 17.8. IR (thin film): max =2941, 1612, 1440, 1241, 1061, 749, 730 cm -1. HRMS (ESI): calculated for C 24 H 24 N 3 O [M+ H] + : 370.1914; found 370.1920. (E)-1-(1-Benzyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (3bg) The general procedure (C) was applied to (E)-1-(1-benzyl-1Hindol-3-yl)-N-(4-methoxyphenyl)methanimine (1b, 170 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 85/15) afforded the title compound (3bg) as a yellow solid (204 mg, 92 %). mp 178-180 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.63 8.59 (m, 2H), 7.23 7.05 (m, 11H), 7.02 6.97 (m, 2H), 6.86 6.82 (m, 2H), 6.82 6.77 (m, 2H), 5.16 (s, 2H), 4.84 (q, J = 7.3 Hz, 1H), 3.73 (s, 3H), 1.61 (d, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 153.3, 148.5, 147.0, 142.2, 137.3, 136.8, 128.7 (2C), 128.6 (2C), 127.4, 127.2 (2C), 126.6, 126.2, 125.8 (2C), 123.0, 122.6, 121.9, 121.8 (2C), 114.2 (2C), 112.2, 109.7, 55.5, 47.3, 35.1, 19.7. IR (thin film): max = 3056, 1614, S30

1423, 1105, 695 cm -1. HRMS (ESI): calculated for C 31 H 29 N 2 O [M+ H] + : 445.2274; found 445.2273. (E)-1-(1,7-Dimethyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (3cg) The general procedure (C) was applied (E)-1-(1,7-dimethyl- 1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1c, 139 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 80/20) afforded the title compound (3cg) as a yellow oil (96 mg, 50 %). 1 H NMR (400 MHz, CDCl 3 ) δ 8.68 (s, 1H), 8.46 (ddd, J = 8.0, 1.3, 0.7 Hz, 1H), 7.31 7.15 (m, 5H), 7.11 7.01 (m, 3H), 6.90 (dt, J = 7.1, 1.2 Hz, 1H), 6.86 6.78 (m, 2H), 5.11 (q, J = 7.4 Hz, 1H), 3.74 (s, 3H), 3.65 (s, 3H), 2.66 (s, 3H), 1.78 (d, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.1, 153.0, 148.5, 147.2, 142.1, 136.4, 128.7 (2C), 127.0 (2C), 126.4, 126.9, 126.2, 121.8 (2C), 121.6, 120.6, 120.1, 114.2 (2C), 111.7, 55.5, 34.3, 34.1, 20.7, 18.3. IR (thin film): max = 2928, 1613, 1538, 1290. 895 cm -1.. HRMS (ESI): calculated for C 26 H 27 N 2 O [M+ H] + : 383.2118; found 383.2113. (E)-1-(5-Methoxy-1-methyl-2-(1-phenylethyl)-1H-indol-3- yl)-n-(4-methoxyphenyl)methanimine (3dg) The general procedure (C) was applied (E)-1-(5-methoxy-1- methyl-1h-indol-3-yl)-n-(4-methoxyphenyl)methanimine (1d, 139 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 80/20) afforded the title compound (3dg) as a yellow oil (189 mg, 95 %). 1 H NMR (400 MHz, CDCl 3 ) δ 8.64 (s, 1H), 8.14 (d, J = 2.5 Hz, 1H), 7.27 7.10 (m, 5H), 7.09 7.02 (m, 3H), 6.87 6.76 (m, 3H), 4.93 (q, J = 7.3 Hz, 1H), 3.83 (s, 3H), 3.72 (s, 3H), 3.35 (s, 3H), 1.75 (d, J = 7.4 Hz, 3H). S31

13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 155.9, 153.1, 148.6, 147.2, 142.0, 132.7, 128.7 (2C), 127.1 (2C), 126.6, 126.4, 121.8 (2C), 114.3 (2C), 112.7, 111.6, 109.6, 104.3, 55.9, 55.5, 34.6, 31.0, 18.7. IR (thin film): max = 3085, 1558, 1158, 1028, 885, 718 cm -1.. HRMS (ESI): calculated for C 26 H 27 N 2 O 2 [M+ H] + : 399.2067; found 399.2078. (E)-1-(5-(Benzyloxy)-1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4- methoxyphenyl)methanimine (3eg) The general procedure (C) was applied to (E)-1-(5- (benzyloxy)-1-methyl-1h-indol-3-yl)-n-(4- methoxyphenyl)methanimine (1e, 186 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 85/15) afforded the title compound (3eg) as a yellow foam (234 mg, 99 %). mp 62-64 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.77 (s, 1H), 8.38 (d, J = 2.6 Hz, 1H), 7.60 7.54 (m, 2H), 7.43 (t, J = 7.5 Hz, 2H), 7.39 7.26 (m, 6H), 7.19 (t, J = 8.3 Hz, 3H), 7.05 (dd, J = 8.8, 2.6 Hz, 1H), 6.99 6.92 (m, 2H), 5.23 (s, 2H), 5.07 (q, J = 7.3 Hz, 1H), 3.87 (s, 3H), 3.49 (s, 3H), 1.89 (d, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 155.0, 153.0, 148.6, 147.2, 142.0, 137.7, 132.8, 128.7 (2C), 128.5 (2C), 127.8 (2C), 127.7, 127.1 (2C), 126.6, 126.4, 121.8 (2C), 114.3 (2C), 113.3, 111.6, 109.6, 105.8, 70.8, 55.5, 34.6, 31.0, 18.7. IR (thin film): max = 3031, 1612, 1497, 1288, 1105, 735 cm -1. HRMS (ESI): calculated for C 32 H 31 N 2 O 2 [M+ H] + : 475.2380; found 475.2395. Methyl (E)-3-(((4-methoxyphenyl)imino)methyl)-1-methyl-2-(1-phenylethyl)-1H-indole-6- carboxylate (3fg) The general procedure (C) was applied to methyl (E)-3-(((4- methoxyphenyl)imino)methyl)-1-methyl-1h-indole-6-carboxylate (1f, 161 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 85/15) afforded the title compound (3fg) as a yellow foam (209 mg, 99 %). mp 68-79 C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.64 (s, 1H), 8.55 (d, J = S32

8.4 Hz, 1H), 7.96 7.92 (m, 1H), 7.86 (dd, J = 8.4, 1.5 Hz, 1H), 7.28 7.20 (m, 2H), 7.21 7.12 (m, 3H), 7.08 7.01 (m, 2H), 6.86 6.77 (m, 2H), 5.03 (q, J = 7.4 Hz, 1H), 3.85 (s, 3H), 3.71 (s, 3H), 3.44 (s, 3H), 1.77 (d, J = 7.3 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 167.9, 157.4, 152.4, 151.0, 146.7, 141.5, 137.1, 129.6, 128.8 (2C), 127.1, 126.8, 124.2, 122.7 (2C), 121.9 (2C), 121.8, 114.3 (2C), 112.1, 111.1, 55.5, 52.0, 34.8, 31.1, 18.5. IR (thin film): max = 2948, 1707, 1567, 1433, 1236, 783 cm -1. HRMS (ESI): calculated for C 27 H 27 N 2 O 3 [M+ H] + : 427.2016; found 427.2020 (E)-3-(((4-Methoxyphenyl)imino)methyl)-1-methyl-2-(1-phenylethyl)-1H-indole-5- carbonitrile (3gg) The general procedure (C) was applied to methyl (E)-3-(((4- methoxyphenyl)imino)methyl)-1-methyl-1h-indole-5-carbonitrile (1g, 144 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 85/15) afforded the title compound (3gg) as a yellow oil (162 mg, 82 %). 1 H NMR (400 MHz, CDCl 3 ) δ 9.08 (dd, J = 1.7, 0.7 Hz, 1H), 8.72 (s, 1H), 7.51 (dd, J = 8.5, 1.7 Hz, 1H), 7.38 7.25 (m, 6H), 7.19 7.11 (m, 2H), 6.96 6.89 (m, 2H), 5.10 (q, J = 7.9 Hz, 1H), 3.83 (s, 3H), 3.52 (s, 3H), 1.88 (d, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.7, 151.6, 150.0, 146.1, 141.1, 139.2, 128.9 (2C), 128.1, 127.0 (2C), 126.9, 125.8, 125.7, 121.9 (2C), 120.7, 114.3 (2C), 112.5, 109.7, 104.6, 55.5, 34.8, 31.2, 18.7. IR (thin film): max = 2942, 2220, 1614, 1500, 1289, 1106 cm -1. HRMS (ESI): calculated for C 26 H 24 N 3 O [M+ H] + : 394.1914; found 394.1909. (E)-1-(5-Fluoro-1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4- methoxyphenyl)methanimine (3hg) The general procedure (c) was applied to (E)-1-(5-fluoro-1- methyl-1h-indol-3-yl)-n-(4-methoxyphenyl)methanimine (1h, 141 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 0.62 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/etoac 90/10) S33