TY - JOUR
T1 - Confined acids catalyze asymmetric single aldolizations of acetaldehyde enolates
AU - Schreyer, Lucas
AU - Kaib, Philip S.J.
AU - Wakchaure, Vijay N.
AU - Obradors, Carla
AU - Properzi, Roberta
AU - Lee, Sunggi
AU - List, Benjamin
N1 - Publisher Copyright:
© 2018 American Association for the Advancement of Science. All Rights Reserved.
PY - 2018
Y1 - 2018
N2 - Reactions that form a product with the same reactive functionality as that of one of the starting compounds frequently end in oligomerization. As a salient example, selective aldol coupling of the smallest, though arguably most useful, enolizable aldehyde, acetaldehyde, with just one partner substrate has proven to be extremely challenging. Here, we report a highly enantioselective Mukaiyama aldol reaction with the simple triethylsilyl (TES) and tert-butyldimethylsilyl (TBS) enolates of acetaldehyde and various aliphatic and aromatic acceptor aldehydes. The reaction is catalyzed by recently developed, strongly acidic imidodiphosphorimidates (IDPi), which, like enzymes, display a confined active site but, like small-molecule catalysts, have a broad substrate scope. The process is scalable, fast, efficient (0.5 to 1.5 mole % catalyst loading), and greatly simplifies access to highly valuable silylated acetaldehyde aldols.
AB - Reactions that form a product with the same reactive functionality as that of one of the starting compounds frequently end in oligomerization. As a salient example, selective aldol coupling of the smallest, though arguably most useful, enolizable aldehyde, acetaldehyde, with just one partner substrate has proven to be extremely challenging. Here, we report a highly enantioselective Mukaiyama aldol reaction with the simple triethylsilyl (TES) and tert-butyldimethylsilyl (TBS) enolates of acetaldehyde and various aliphatic and aromatic acceptor aldehydes. The reaction is catalyzed by recently developed, strongly acidic imidodiphosphorimidates (IDPi), which, like enzymes, display a confined active site but, like small-molecule catalysts, have a broad substrate scope. The process is scalable, fast, efficient (0.5 to 1.5 mole % catalyst loading), and greatly simplifies access to highly valuable silylated acetaldehyde aldols.
UR - http://www.scopus.com/inward/record.url?scp=85054773431&partnerID=8YFLogxK
U2 - 10.1126/science.aau0817
DO - 10.1126/science.aau0817
M3 - Article
C2 - 30309951
AN - SCOPUS:85054773431
SN - 0036-8075
VL - 362
SP - 216
EP - 219
JO - Science
JF - Science
IS - 6411
ER -