Two previously undescribed monoterpenoid indole alkaloids, N -formylyunnanensine ( 1 ) and scholaphylline ( 2 ), along with eight known alkaloids, namely, 19,20- E -vallesamine ( 3 ), 19,20- Z -vallesamine ( 4 ), 19,20- E -valles- amine N -oxide ( 5 ), 6,7- seco -19,20 alpha-epoxyangustilobine B ( 6 ), 16 R -19,20- E -isositsirikine ( 7 ), N -demethylal- stogustine N -oxide ( 8 ), E -vallesiachotamine ( 9 ), and Z -vallesiachotamine ( 10 ), were isolated from the bark of Alstonia scholaris. Alkaloid 1 was determined to be the N -formyl derivative of the known alkaloid, yunnanensine, comprising a pair of inseparable E / Z -formamide rotamers, while scholaphylline ( 2 ) was identified as the first member of the seco stemmadenine-yunnanensine type bisindole alkaloid. The structures of these alkaloids and their absolute configurations were established based on detailed analysis of the spectroscopic data in conjunction with the TDDFT-ECD method. A possible biogenetic pathway to 1 and 2 , involving stemmadenine as the primary precursor, was proposed. Scholaphylline ( 2 ) showed modest cytotoxicity against Panc1 (IC 50 27.7 +/- 5.1 mu M), MDA-MB-231 (IC 50 32.0 +/- 2.2 mu M), and MDA-MB-468 (IC 50 34.1 +/- 3.3 mu M) cancer cell lines, while N -for- mylyunnanensine ( 1 ) did not show appreciable cytotoxicity against any of the tested cell lines.