Rh-catalyzed C–C bond cleavage by transfer hydroformylation by Stephen K. Murphy, Jung-Woo Park, Faben A. Cruz, and Vy M. Dong Science Volume 347(6217):56-60 January 2, 2015 Published by AAAS

Fig. 1 Dehydroformylation in nature and organic synthesis Fig. 1 Dehydroformylation in nature and organic synthesis.(A) Dehydroformylation during sterol biosynthesis. Dehydroformylation in nature and organic synthesis.(A) Dehydroformylation during sterol biosynthesis. (B) Reactivity of acyl-RhIII-hydrides. (C) Proposed transfer hydroformylation. Stephen K. Murphy et al. Science 2015;347:56-60 Published by AAAS

Fig. 2 Effects of counterion structure and ring strain Fig. 2 Effects of counterion structure and ring strain.Yields were determined by gas chromatographic analysis of the reaction mixtures using durene as an internal standard. nbd, norbornadiene; nbe, norbornene; bnbd, benzonorbornadiene. Effects of counterion structure and ring strain.Yields were determined by gas chromatographic analysis of the reaction mixtures using durene as an internal standard. nbd, norbornadiene; nbe, norbornene; bnbd, benzonorbornadiene. Stephen K. Murphy et al. Science 2015;347:56-60 Published by AAAS

Fig. 3 Applications of dehydroformylation Fig. 3 Applications of dehydroformylation.(A) General conditions for transfer hydroformylation. Applications of dehydroformylation.(A) General conditions for transfer hydroformylation. (B) Substrate scope. (C) Natural product derivatization. (D) Three-step synthesis of (+)-yohimbenone. Yields are of isolated materials and mixtures of regioisomers where indicated. rr is the regioisomeric ratio; rr values were determined by 1H NMR analysis of the reaction mixtures. The yields of 2e and 2k were determined by 1H NMR analysis of the reaction mixtures using durene as an internal standard. See the supplementary materials for details. Stephen K. Murphy et al. Science 2015;347:56-60 Published by AAAS

Fig. 4 Mechanistic studies.(A) Deuterium labeling studies. Mechanistic studies.(A) Deuterium labeling studies. (B) Isolation of organometallic intermediates. (C) Proposed catalytic cycle. Stephen K. Murphy et al. Science 2015;347:56-60 Published by AAAS