Supporting Information

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1 Supporting Information Wiley-VCH Weinheim, Germany

2 A Versatile Hexadiene Synthesis via Decarboxylative sp -sp Coupling/Cope Rearrangement. Shelli R. Waetzig, Dinesh K. Rayabarapu, Jimmie D. Weaver, and Jon A. Tunge Department of Chemistry, University of Kansas, Lawrence, Kansas Experimental Materials. Methylene Chloride and toluene were dried over activated alumina. All other materials were used as received. Linear β-ketoesters were prepared by DMAP-catalyzed addition of diketene to the corresponding allylic alcohols. Cyclic β- ketoesters were prepared DMAP catalyzed condensation of ß-ketomethylesters and allylic alcohols. Alkylation of linear β- ketoesters was achieved using t BuOK and the corresponding alkylating agent. Vinylation of β-ketoesters to afford substrates was achieved using In(OTf) catalyzed addition of alkynes. Alkylidene malononitrile substrates were prepared via Knoevenagel condensation of malononitrile with β-ketoesters. H NMR and C NMR spectra were obtained on a Bruker Avance or a Bruker Avance DRX spectrometer and referenced to residual protio solvent signals. Structural assignments are based on H, C, DEPT-, COSY, HSQC, and sel-noe spectroscopies. General Procedure for the Palladium-Catalyzed Decarboxylation of vinylic b-ketoesters: A round-bottom side-arm flask ( ml) containing Pd(PPh ) (. mmol,. mol%) was evacuated and purged with argon gas. An allylic β-ketoester (. mmol) and dichloromethane were added to the system and the reaction mixture was stirred at room temperature for.-. h. Next, the reaction mixture was diluted with dichloromethane and filtered through a short Celite and silica gel pad. The filtrate was concentrated and the residue was purified on a silica gel column using hexane-dichloromethane (:) as eluent to afford the decarboxylative coupling products. General Procedure for the Palladium-Catalyzed Decarboxylation of Alkylidene Malononitriles: In a dried Schlenk flask under argon, Pd(PPh ) (. mmol) was added to substrates (. mmol) dissolved in methylene chloride ( ml). Reactions were stirred at room temperature for - hours. The reaction mixture was then concentrated and directly purified via flash chromatography (SiO, % EtOAc:Hexane). Conditions and results for the Cope Rearrangents of the a-allylation products. Table. Cope Rearrangement of,-dienes. a Substrate conditions Yield % O Ph a O Ph n-c H a i b µw, C, min mol% PdCl (CH CN) C, hrs µw, C, min. µw, C, min. b µw, C, min..: d.r. e e mol% PdCl (CH CN) C, hrs.: d.r. Supporting information for this article is available on the WWW under or from the author.

3 µw, C, min..: d.r. f µw, C, min. h µw, C, min. c k [a] All µw reactions run at.m in CH CN, all Pd(II)-catalyzed reactions run in CH Cl. [b] ~: E/Z mix [c] Starting material and product contaminated with ca. % monomethylated f O Ph (a): H NMR ( MHz, CDCl ): δ =. (s, H),.-. (m, H),.-. (m, H),. (s, H),.-. (m, H),. (d, J =. Hz, H),.-. (m, H).. (dd, J =. Hz, J =. Hz, H),.-. (m, H),.-. (m, H); C{ H} NMR ( MHz, CDCl ): δ =.,.,.,.,.,.,.,.,.,.,.,.,.; IR (neat)? max :,,,,,,,,,,,,, cm - ; HRMS calcd for (M+H) C H O., found (M+H) C H O..

4 O Ph Ph (b): H NMR ( MHz, CDCl ): δ =. (s, H),. (dd, J =. Hz, J =. Hz, H),. (dd, J =. Hz, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (dd, J =. Hz, J =. Hz, H),. (s, H),. (s, H),.-. (m, H),.-. (m, H),.-. (m, H),.-. (m, H); C{ H} NMR ( MHz, CDCl ): δ =.,.,.,.,...,.,.,.,.,.,.,.,.,.,.,.; IR (neat)? max :,,,,,,,,,,,,,, cm - ; HRMS calcd for (M+H) C H O., found (M+H) C H O..

5 O (c): H NMR ( MHz, CDCl ): δ =. (t, J =. Hz, H),. (t, J =. Hz, H),.-. (m, H),.-. (m, H),.-. (m, H),. (s, H),. (d, J =. Hz, H),.-. (m, H),. (s, H),. (s, H),.-. (m, H); C{ H} NMR ( MHz, CDCl ): δ =.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.; IR (neat)? max :,,,,,,,,,,, cm - ; HRMS calcd for (M+H) C H O., found (M+H) C H O..

6 O H C (d): H NMR ( MHz, CDCl ): δ =. (t, J =. Hz, H),. (s, H),.-. (m, H),.-. (m, H),.. (m, H),. (s, H),.-. (m, H),.-. (m, H),.-. (m, H); C{ H} NMR ( MHz, CDCl ): δ =.,.,.,.,.,.,.,.,.,.,.,.,.,.,.; IR (neat)? max :,,,,,,,,,,,, cm - ; HRMS calcd for (M+H) C H O., found (M+H) C H O..

7 O (e): H NMR ( MHz, CDCl ): δ =. (s, H),. (s, H),. (dd, J =. Hz, J =. Hz, H),. (dd, J =. Hz, J =. Hz, H),. (dt, J =. Hz, J =. Hz, H),. (dt, J =. Hz, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),.-. (m, H),. (dd, J =. Hz, J =. Hz, H); C{ H} NMR ( MHz, CDCl ): δ =.,.,.,.,.,.,.,.,.; IR (neat)? max :,,,,,,,,, cm - ; HRMS calcd for (M+NH ) C H ON., found (M+NH ) C H ON..

8 O (f): H NMR ( MHz, CDCl ): δ =. (t, J =. Hz, H),.-. (m, H),.-. (m, H),.. (m, H),. (t, J =. Hz, H),.-. (m, H),. (s, H),. (s, H),.-. (m, H),. (m, H); C{ H} NMR ( MHz, CDCl ): δ =.,.,.,.,...,.,.,.,.,.,.,.,.,.,.; IR (neat)? max :,,,,,,,,,,,,, cm - ; HRMS calcd for (M+H) C H O., found (M+H) C H O..

9 O (g): H NMR ( MHz, CDCl ): δ =.-. (m, H),. (m, H),.-. (m, H),.-. (m, H),. (dt, J =. Hz, J =. Hz, H),. (dd, J =. Hz, J =. Hz, H),. (dd, J =. Hz, J =. Hz, H),. (d, J =. Hz, H),.-. (m, H),. (dd, J =. Hz, J =. Hz, H); C{ H} NMR ( MHz, CDCl ): δ =.,.,.,.,.,.,.,.,.,.,.; IR (neat)? max :,,,,,,,,,,,, cm - ; HRMS calcd for (M+H) C H O., found (M+H) C H O..

10 O (h): H NMR ( MHz, CDCl ): δ =.-. (m, H),.-. (m, H),.-. (m, H),.-. (m, H),. (dt, J =. Hz, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),.-. (m, H),. (dd, J =. Hz, J =. Hz, H); C{ H} NMR ( MHz, CDCl ): δ =.,.,.,.,.,.,.,.,.,.; IR (neat)? max :,,,,,,,, cm - ; HRMS calcd for (M+) C H O., found (M+) C H O..

11 O Ph (i): H NMR ( MHz, CDCl ): δ =. (t, J =. Hz, H).-. (m, H),. (q, J =. Hz, H),. (q, J =. Hz, H),. (q, J =. Hz, H),. (s, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (s, H),.-. (m, H),. (dddd, J =. Hz, J =. Hz, J =. Hz, J =. Hz, H),. (d, J =. Hz, H),.-. (m, H); C{ H} NMR ( MHz, CDCl ): δ =.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.; IR (neat)? max :,,,,,,,,, cm - ; HRMS calcd for (M+) C H O., found (M+H) C H O..

12 O Ph (a): pale yellow oil: H NMR ( MHz, CDCl ) d. (q, H: J =. Hz, CH =CHCH ),. (d, H: J =. Hz, CH COR),. (q, H: J =. Hz, R C=CHCH ),. (s, H: PhCH R),. (m, H: CH =CHR),. (m, H: CH =CHR),. (dt, H: J =.,. Hz, R C=CHR),. (m, H: Ph-H),. (m, H: Ph-H); Selective noe irradiation of the resonance at d. ppm produces a large enhancement in the allylic proton resonance at d. ppm, consistent with an E- geometry. C NMR ( Hz, CDCl ) d. (CH COR),. (CH CH=CR ),. (RCH Ph),. (RCHCH=CH ),. (CH =CHR),. (Ph-CH),. (Ph-CH),. (Ph-CH),. (CH =CHR),. (quat. C),. (quat. C),. (R C=CHR),. (C=O); IR (CH Cl )? max :,, ; HRMS calcd for [M+H]., found..

13 O ~: mixture of cis:trans isomers (c): pale yellow oil: H NMR ( MHz, CDCl ) d. (dt, H: J =.,. Hz, CH -hexyl),. (t, H: J =. Hz, RCH CH ),. (m, H: n-hexyl CH ),. (m, H: n-hexyl CH s),. (s, H: n-hexyl CH ),. (dd, H: J =.,. Hz, n-hexyl CH ),. (t, H: J =. Hz, CH =CHCH CH ),. (d, H: J =.Hz, CH COR),. (m, H: R C=CRCH CH ),. (m, H: RCH=CH ),. (m, H: RCH=CH ); C NMR ( Hz, CDCl ) d.,. (CH CH CR=CR ),. (CH -n-hexyl),.,. (R C=CRCH CH ),. (n-hexyl CH ),.,. (n-hexyl CH ),.,. (n-hexyl CH ),.,. (CH ),. (allylic CH ),.,. (allylic CH ),.,. (n-hexyl CH ),.,. (allylic CH ),. (allylic CH ),.,. (RCH=CH ),.,. (RCH=CH ),.,. (CH COCR=CR ),.,. (CH COCR=CR ),.,. (C=O); IR (CH Cl )? max :,,, ; HRMS calcd for [M+H]., found.. O Ph ~: mixture of cis:trans isomers

14 (i): pale yellow oil: H NMR ( MHz, CDCl ) d. (m, H: CH CH R),. (m, H: n-hexyl CH s),. (m, H: n- hexyl CH),. (m, H: n-hexyl CH),. (d, H: J =. Hz, CH COR),.-. (m, H: allylic CH s),. (d, H: J =. Hz, RCH Ph),. (m, H: RCH=CH ),. (m, H: RCH=CH ),. (m, H: Ph-H),. (m, H: Ph-H),. (m, H: Ph-H); C NMR ( Hz, CDCl ) d.,. (CH -n-hexyl),.,. (n-hexyl CH ),.,. (n-hexyl CH ),.,. (n-hexyl CH ),.,. (CH COR),.,. (n-hexyl CH ),.,. (allylic CH ),.,. (allylic CH ),.,. (allylic CH ),. (RCH Ph),.,. (RCH=CH ),., (Ph-CH),.,. (Ph- CH),. (Ph-CH),.,. (RCH=CH ),.,. (quat. C),.,. (quat. C),.,. (quat. C),.,. (C=O); IR (CH Cl )? max :,, ; HRMS calcd for [M+H]., found.. H A H B (a): colorless oil: H NMR ( MHz, CDCl ) d. (m, H: cyclohexyl CH s),. (pd, H: J =.,. Hz, cyclohexyl CH s),. (m, H: cyclohexyl CH s),. (d, H: allylic CH ),. (d, H: J =. Hz, H A ),. (d, H: J =. Hz, H B ),. (m, H: CH=CH ),. (app. d, H: J =. Hz, CH=CRC(CN) ); C NMR ( Hz, CDCl ) d. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (allylic CH ),. (C(CN) ),. (CN),. (CH=CH ),. (CH=CRC(CN) ),. (CH=CH ),. (CH=CRC(CN) ); IR (CH Cl )? max :,,,, ; HRMS calcd for C H N [M+]:., found:..

15 H A H B (b): colorless oil: H NMR ( MHz, CDCl ) d. (m, H: cycloheptyl CH ),. (m, H: cycloheptyl CH ),. (m, H: cycloheptyl CH ),. (m, H: cycloheptyl CH ),. (m, H: cycloheptyl CH ),. (d, H: J =. Hz, (CN) CCH ),. (dq, H: J =.,. Hz, H A ),. (dd, H: J =.,. Hz, H B ),. (dddd, H: J =.,.,.,. Hz, CH=CH ),. (t, H: J =. Hz, CH=CR ); C NMR ( Hz, CDCl ) d. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. ((CN) CCH ),. (C(CN) ),. (CN),. (CH=CH ),. (CH=CH ),. (CH=CR ),. (CH=CR ); IR (CH Cl )? max :,,, ; HRMS calcd for C H N [M+]:., found:..

16 (c): colorless oil: H NMR ( MHz, CDCl ) d. (d, H: J =. Hz, CH CHR ),. (m, H: cyclohexyl CH s),. (m, H: cyclohexyl CH s),. (dd, H: J =.,. Hz, CH CH=CHR),. (m, H: cyclohexyl CH s),. (m, H: cyclohexyl CH s),. (p, H: J =. Hz, CH CHR ),. (ddq, H: J =.,.,. Hz, CH=CHCH ),. (dq, H: J =.,. Hz, CH CH=CH),. (app. s, H: CH=CRC(CN) ; C NMR ( Hz, CDCl ) d. (CH CHR ),. (CH CH=CHR),. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (CH CHR ),. (C(CN) ),. (CN),. (CN),. (CH=CR ),. (CH=CHCH ),. (CH CH=CHR),. (CH=CRC(CN) ); IR (CH Cl )? max :,, ; HRMS calcd for C H N [M+]:., found:..

17 (d): colorless oil: H NMR ( MHz, CDCl ) d. (d, H: J =. Hz, CH CHR ),. (m, H: cycloheptyl CH ),. (sext, H: J =. Hz, cycloheptyl CH s),. (dd, H: J =.,. Hz, CH CHR ),. (m, H: cycloheptyl CH s),. (m, H: cycloheptyl CH s),. (p, H: J =. Hz, CH CHR ),. (ddq, H: J =.,.,. Hz, CH=CHCH ),. (ddq, H: J =.,.,. Hz, CH CH=CHR),. (t, H: J =. Hz, CH=CR ); C NMR ( Hz, CDCl ) d. (CH CHR ),. (CH CH=CHR),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (CH CHR ),. (C(CN) ),. (CN),. (CN),. (CH CH=CHR),. (CH CH=CHR),. (CH=CR ),. (CH=CR ); IR (CH Cl )? max :,, ; HRMS calcd for C H N [M+]:., found:..

18 (e): colorless oil: major diastereomer: H NMR ( MHz, CDCl ) d. (d, H: J =. Hz, CH CH=CHR),. (m, H: CH CH=CHR and CH CR=CHR),. (t, H: J =. Hz, CH CH=CR ),. (p, H: J =. Hz, CH CHCH=CHR),. (ddq, H: J =.,.,. Hz, RCH=CHCH ),. (ddd, H: J =.,.,. Hz, CH CH=CHR),. (dq, H: J =.,. Hz, CH CH=CR ); Selective noe irradiation of the resonance at the vinyl resonance at d. ppm shows only small enhancement of the methyl doublet at d. ppm, consistent with the E-geometry. C NMR ( Hz, CDCl ) d. (CH CH=CR ),. (CH CR=CHR),. (CH CHR ),. (CH CH=CHR),. (CH CHR ),. (C(CN) ),. (CN),. (CN),. (CH CR=CHR),. (CH CH=CHR),. (CH CH=CR ),. (CH CH=CHR); IR (CH Cl )? max :,, ; HRMS calcd for C H N [M+]., found:..

19 (f): colorless oil: major diastereomer: H NMR ( MHz, CDCl ) d. (m, H: cyclohexyl CH s),. (dd, H: J =.,. Hz, CH CH),. (s, H: CH CR ),. (m, H: cyclohexyl CH s),. (m, H: cyclohexyl CH),. (app. s, H: CH=CHCHR ),. (dp, H: J =.,. Hz, CH=CHCHR ),. (m, H: CH=CHCHR ),. (qq, H: J =.,. Hz, CH CH=CR ); Selective noe irradiation of the CH CH=CR resonance at d. ppm gives strong enhancement of the methyl group at d. ppm, but no enhancement of the CH C(R)= resonance, consistent with the E-geometry. C NMR ( Hz, CDCl ) d. (CH CR ),. (CH CHR),. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (CH=CHCHR ),. (C(CN) ),. (CN),. (CN),. (CH=CHCHR ),. (CH CR=CHR),. (CH CH=CR ),. (CH=CHCHR ); IR (CH Cl )? max :,,, ; Anal. Calcd for C H N : C,.; H,.; N,.. Found: C,.; H,.; N,..

20 H A H B Ph (g): colorless oil: H NMR ( MHz, CDCl ) d. (s, H: CH CR=CH ),. (s, H: CH CR=CHR),. (s, H: allylic CH ),. (d, H: J =. Hz, RCH Ph),. (s, H: H A ),. (app. t, H: J =. Hz, H B ),. (tq, H: J =.,. Hz, PhCH CH=CR ),. (d, H: J =. Hz, Ph-H),. (m, H: Ph-H). (app. t, H: J =. Hz, Ph-H); C NMR ( Hz, CDCl ) d. (CH CRC(CN) ),. (CH CR=CH ),. (CH Ph),. (C(CN) ),. (CH CR=CH ),. (CN),. (R C=CH ),. (CH CR=CHR),. (Ph-CH),. (Ar-CH),. (Ar-CH),. (CH=CRC(CN) ),. (R C=CH ),. (quat. Ar-C); IR (CH Cl )? max :,, ; HRMS calcd for C H N [M+]., found:..

21 H A H B (h): colorless oil: H NMR ( MHz, CDCl ) d. (dd, H: J =.,. Hz, CH CH=CR ),. (app. t, H: J =. Hz, CH CR=C(CN) ),. (s, H: CH CR=CH ),. (s, H: allylic CH ),. (app. s, H: H A ),. (p, H: J =. Hz, H B ),. (qq, H: J =.,. Hz, CH CH=CR ); C NMR ( Hz, CDCl ) d. (CH CR=CHR),. (CH CH=CR ),. (CH CR=CH ),. (C(CN) ),. (allylic CH ),. (CN),. (R C=CH ),. (CH CR=CHR),. (CH CH=CR ),. (CR =CH ); IR (CH Cl )? max :,,, ; HRMS calcd for C H N [M+]., found:..

22 Ph (i): white solid: H NMR ( MHz, CDCl ) d. (dd, H: J =.,. Hz, CH CH=CR ),. (t, H: J =. Hz, CH CR=CHR),. (dd, H: J =.,. Hz, allylic CH ),. (qq, H: J =.,. Hz, CH CH=CR ),. (dt, H: J =.,. Hz, CH=CHPh),. (d, H: J =. Hz, Ph-H),. (t, H: J =. Hz, Ph-H),. (d, H: J =. Hz, Ph-H); C NMR ( Hz, CDCl ) d. (CH CR=CHR),. (CH CHR),. (CH CH=CHPh),. (C(CN) ),. (CN),. (CH=CHPh),. (quat Ar-C),. (Ph-CH),. (CH CHR),. (Ph-CH),. (Ph-CH),. (R C=CH ),. (CH=CHPh); IR (CH Cl )? max :,,,,,,,,,, ; HRMS calcd for C H N [M+]., found:..

23 (j): colorless oil: H NMR ( MHz, CDCl ) d. (app. d, H: J =. Hz, CH CR=CHR),. (app. d, H: J =. Hz, CH CH=CR ),. (dd, H: J =.,. Hz, allylic CH ),. (m, H: CH=CH ),. (m, H: CH=CH ),. (app. q, H: J =. Hz, CH CH=CR ); C NMR ( Hz, CDCl ) d. (CH CH=CR ),. (CH CR=CHR),. (allylic CH ),. (C(CN) ),. (CN),. (R C=CH ),. (CHR=CR ),. (CH CH=CR ),. (CH=CH ); IR (CH Cl )? max :,,, ; HRMS calcd for C H N [M+]., found:.. + contaminant : ratio of dimethylated : monomethylated product, inseparable mixture.

24 (k): colorless oil: H NMR ( MHz, CDCl ) d. (m, H: cyclohexyl CH),. (m, H: cyclohexyl CH ),. (d, H: J =. Hz, one of (CH ) C=CR ),. (app. t, H: J =. Hz, one of (CH ) C=CR ),. (app. d, H: J =. Hz, cyclohexyl CH),. (m, H: cyclohexyl CH),. (m, H: cyclohexyl CH ),. (m, H: CHCH=CH),. (dp, H: J =.,. Hz, CH=CHCHR ),. (m, H: CH=CHCHR ); C NMR ( Hz, CDCl ) d. (one of CH ),. (cyclohexyl CH ),. (one of CH ),. (one of CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (CH=CHCHR ),. (CR (CN) ),. (CN),. (CN),. (RC(CH ) ),. (CHCH=CH),. (CHCH=CH),. (R C=C(CH ) ); IR (CH Cl )? max :,,,,,,, ; HRMS calcd for C H N [M+]., found:.. CN H A H B

25 (a): colorless oil: H NMR ( MHz, CDCl ) d. (m, H: cyclohexyl CH),. (m, H: cyclohexyl CH s),. (m, H: cyclohexyl CH),. (m, H: cyclohexyl CH),. (m, H: one of cyclohexyl CH and allylic CH ),. (d, H: J =. Hz, cyclohexyl CH),. (app. s, H: (CN) C=C-CHR ),. (dq, H: J =.,. Hz, H A ),. (d, H: J =. Hz, H B ),. (dddd, H: J =.,.,.,. Hz, RCH=CH ); C NMR ( Hz, CDCl ) d. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (allylic CH ),. ((CN) C=CRCHR ),. ((CN) C=C),. (CN),. (C=CH ),. (CH=CH ),. (R C=C(CN) ); IR (CH Cl )? max :,,, ; HRMS calcd for C H N [M+]., found:.. CN H A H B

26 (b): colorless oil: H NMR ( MHz, CDCl ) d. (app. q, H: J =. Hz, cycloheptyl CH),. (m, H: cycloheptyl CH s),. (m, H: cycloheptyl CH s),. (m, H: cycloheptyl CH),. (m, H: one of cycloheptyl CH and one of allylic CH ),. (m, H: one of cycloheptyl CH and one of allylic CH ),. (ddd, H: J =.,.,. Hz, cycloheptyl CH),. (m, H: (CN) C=CRCHR ),. (dq, H: J =.,. Hz, H A ),. (app. d, H: J =. Hz, H B ),. (dddd, H: J =.,.,.,. Hz, RCH=CH ); C NMR ( Hz, CDCl ) d. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (allylic CH ),. ((CN) C=CRCHR ),. ((CN) C=C),. (CN),. (CN),. (C=CH ),. (CH=CH ),. (R C=C(CN) ); IR (CH Cl )? max :,,,, ; HRMS calcd for C H N [M+]., found.. CN

27 (c): colorless oil: H NMR ( MHz, CDCl ) d. (d, H: J =. Hz, CH CHR ),. (m, H: cyclohexyl CH s),. (dd, H: J =.,. Hz, CH CH=CHR),. (m, H: cyclohexyl CH ),. (td, H: J =.,. Hz, cyclohexyl CH),. (m, H: R CHCH ),. (d, H: J =. Hz, (CN) C=CRCH),. (d, H: J =. Hz, cyclohexyl CH),. (ddd, H: J =.,.,. Hz, CH CH=CHR),. (dq, H: J =.,. Hz, CH CH=CHR); C NMR ( Hz, CDCl ) d. (CH CH=CHR),. (CH CHR ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (CH CHR ),. ((CN) C=CRCH),. (C=C(CN) ),. (CN),. (CN),. (CH CH=CHR),. (CH CH=CHR),. (R C=C(CN) ); IR (CH Cl )? max :,,, ; Anal. Calcd For C H N : C,.; H,.; N,.. Found: C,.; H,.; N,.. CN

28 (d): colorless oil: H NMR ( MHz, CDCl ) d. (m, H: cycloheptyl CH),. (d, H: J =. Hz, CH CHR ),. (m, H: cycloheptyl CH s),. (dd, H: J =.,. Hz, CH CH=CHR),. (m, H: cycloheptyl CH s),. (m, H: cycloheptyl CH s),. (q, H: J =. Hz, cycloheptyl CH s),. (td, H: J =.,. Hz, cycloheptyl CH),. (ddd, H: J =.,.,. Hz, cycloheptyl CH),. (m, H: CH CHRCHR ). (ddq, H; J =.,.,. Hz, CH CH=CH),. (dq, H: J =.,. Hz, CH CH=CH); C NMR ( Hz, CDCl ) d. (CH CH=CH),. (CH CHR ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (cycloheptyl CH ),. (CH CHR ),. (CH CHRCHR ),. (C(CN) ),. (CN),. (CN),. (CH=CHCH ),. (CH CH=CHR),. (C=C(CN) ),; IR (CH Cl )? max :,,,, ; HRMS calcd for C H N [M+]., found:.. CN (absolute configuration unknown)

29 (e): colorless oil: H NMR ( MHz, CDCl ) d. (d, H: J =. Hz, CH CHRCH=CHR),. (d, H: J =. Hz, CH CHR ),. (dd, H: J =.,. Hz, CH CH=CHR),. (m, H: CH CR=C(CN) and CH CHRCH=CHR),. (m, H: CH CHR ),. (ddd, H: J =.,.,. Hz, RCH=CHCH ),. (dq, H: J =.,. Hz, CH CH=CHR); C NMR ( Hz, CDCl ) d. (CH CHR ),. (CH CH=CHR),. (CH CR=C(CN) ),. (CH CHRCH=CHR),. (CH CHRCH=CHR),. (CH CHR ),. (C(CN) ),. (CN),. (CN),. (CH CH=CHR),. (CH CH=CHR),. (R C=C(CN) ); IR (CH Cl )? max :, ; HRMS calcd for C H N [M+]., found:.. Enantiomeric ratio determined by GC using a Chiraldex B-DM column. Init. Temp. C, ramp o C/min., final temp. o C. Retention times are. min. and. min. CN

30 (f): colorless oil: H NMR ( MHz, CDCl ) d. (m, H: cyclohexyl CH),. (d, H: J =. Hz, CH CHR ),. (m, H: cyclohexyl CH s),. (m, H: cyclohexyl CH),. (m, H: cyclohexyl CH ),. (m, H: R CHCH=CHR),. (s, H: CH CR=C(CN) ),. (dd, H: J =.,. Hz, CH CHR ),. (dq, H: J =.,. Hz, RCH=CHCHR ),. (dddd, H: J =.,.,.,. Hz, RCHCH=CHR); C NMR ( Hz, CDCl ) d. (CH CHR ),. (CH CR=C(CN) ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (R CHCH=CHR),. (CH CHR ),. ((CN) C),. (CN),. (CN). (R CHCH=CHR),. (R CHCH=CHR),. (R C=C(CN) ); IR (CH Cl )? max :,,,, ; HRMS calcd for C H N [M+]., found:.. CN Ph

31 (g): colorless oil: H NMR ( MHz, CDCl ) d. (s, H: CH CR=CH ),. (s, H: CH CR=C(CN) ),. (dd, H: J =.,. Hz, CHHCR=CH ),. (dd, H: J =.,. Hz, CHHCR=CH ),. (dd, H: J =.,. Hz, CHHPh),. (dd, H: J =.,. Hz, CHHPh),. (dddd, H: J =.,.,.,. Hz, CHCH Ph),. (s, H: CR =CHH),. (s, H: CR =CHH). (d, H: J =. Hz, Ph-H),. (app. t, H: J =. Hz, Ph-H),. (app. t, H: J =. Hz, Ph-H); C NMR ( Hz, CDCl ) d. (CH CR=C(CN) ),. (CH CR=CH ),. (CH Ph),. (CH CR=CH ),. (R CHCH Ph),. (R C=C(CN) ),. (CN),. (CN),. (R C=CH ),. (Ph-CH),. (Ph-CH),. (Ph-CH),. (quat. Ph-C),. (R C=CH ),. (R C=C(CN) ; IR (CH Cl )? max :,,,,, ; HRMS calcd for C H N [M+]., found:.. CN

32 (h): colorless oil: H NMR ( MHz, CDCl ) d. (dd, H: J =.,. Hz, CH CHR ),. (s, H: CH CR=CH ),. (d, H: J =. Hz, CH CR=C(CN) ),. (d, H: J =. Hz, CH =CHRCH ),. (dsext., H: J =.,. Hz, CH CHRCH ),. (s, H: R C=CHH),. (s, H: R C=CHH); C NMR ( Hz, CDCl ) d. (CH CR=C(CN) ),. (CH CHRCH ),. (CH CR=CH ),. (CHCH ),. (CH =CHRCH ),. (R C=C(CN) ),. (CN),. (CN),. (R C=CH ),. (CH =CR ),. (R C=C(CN) ); IR (CH Cl )? max :,,, ; Anal. Calcd for C H N : C,.; H,.; N,.. Found: C,.; H,.; N,.. CN Ph

33 (i): pale yellow oil: H NMR ( MHz, CDCl ) d. (dd, H: J =.,. Hz, CH CHR ),. (d, H: J =. Hz, CH CR=C(CN) ),. (m, H: CHHCH=CHPh),. (m, H: CHHCH=CHPh),. (dsext, H: J =.,. Hz, CHCH ),. (m, H: CH=CHPh),. (d, H: J =. Hz, CH=CHPh),. (m, H: Ph-H); C NMR ( Hz, CDCl ) d. (CH CR=C(CN) ),. (CH CH),. (CH CH=CHPh),. (CHCH=CHPh),. (R C=C(CN),. (CN),. (CN),. (CH=CHPh),. (Ph-CH),. (Ph-CH),. (Ph-CH),. (CH=CHPh),. (quat. Ph-C),. (R C=C(CN) ); IR (CH Cl )? max :,, ; HRMS calcd for C H N [M+]., found:.. CN H A H B

34 (j): colorless oil: H NMR ( MHz, CDCl ) d. (d, H: J =. Hz, CH CH),. (s, H: CH CR=C(CN) ),. (m, H: CH =CHCHH),. (m, H: CH =CHCHH),. (d, H: J =. Hz, H A ),. (d, H: J =. Hz, H B ),. (m, H: CH=CH ); C NMR ( Hz, CDCl ) d. (CH CR=C(CN) ),. (CH CH),. (allylic CH ),. (CH CHR ),. (C(CN) ),. (CN),. (CN),. (CH=CH ),. (CH=CH ),. (C=C(CN) ); IR (CH Cl )? max :,,,, ; HRMS calcd for C H N [M+]., found:.. CN CN : H contaminant : ratio of dimethylated : monomethylated product, inseparable mixture

35 (k): colorless oil: H NMR ( MHz, CDCl ) d. (s, H: one of R C(CH ) ),. (s, H: one of R C(CH ) ),. (m, H: cyclohexyl CH),. (m, H: cyclohexyl CH s),. (m, H: cyclohexyl CH),. (m, H: cyclohexyl CH ),. (s, H: CH CR=C(CN) ),. (m, H: RCH=CHCHR ),. (dp, H: J =.,. Hz, RCH=CHCHR ),. (m, H: RCHCH=CHR); C NMR ( Hz, CDCl ) d. (cyclohexyl CH ),. (one of (CH ) CR ),. (CH CR=C(CN) ),. (one of (CH ) CR ),. (cyclohexyl CH ),. (cyclohexyl CH ),. (cyclohexyl CH),. (R C(CH ) ),. ((CN) C),. (CN),. (CN),. (R CHCH=CHR),. (R CHCH=CHR),. (R C=C(CN) ); IR (CH Cl )? max :,,,,,,, ; HRMS calcd for C H N [M+]., found:..